bluuebunny/crossref_metadata_2025 huggingface dataset:
Functional Group Interconversion
Authors: Lambert Tristan H.
Published: November 2020

David Milstein at the Weizmann Institute of Science reported (Angew. Chem. Int. Ed. 2013, 52, 6269) the unusual deamination of amine 1 to alcohol 3 catalyzed by ruthenium complex 2. In the reverse sense, Qing Xu at Wenzhou University found (Adv. Synth. Cat. 2013, 355, 73) that the conversion of benzyl alcohol (4) to sulfonamide 5 was catalyzed by benzaldehyde and catalytic potassium carbonate. Gold(I) catalysis was utilized (Chem. Commun. 2013, 49, 4262) by Ai-Lan Lee at Heriot-Watt University for the direct etherification of allylic alcohol 6 with isopropanol to produce 7. Tobias Ritter at Harvard demonstrated (J. Am. Chem. Soc. 2013, 135, 2470) that the reagent PhenoFluor (9) developed in his laboratory displays astonishing selectivity for the late-stage deoxyfluorination of complex alcohols and polyols, including glucopyranoside 8 to produce 10. A Mitsunobu protocol for the conversion of alcohol 11 to ester 13 using catalytic amounts of the hydrazide 12 and iron(II) phthalocyanine was developed (Angew. Chem. Int. Ed. 2013, 52, 4613) by Tsuyoshi Taniguchi at Kanazawa University. We reported (Org. Lett. 2013, 15, 38) a Mitsunobu-like inversion of alcohol 14 to mesylate 16 catalyzed by diphenylcyclopropenone 15. Domingo Gomez Pardo and Janine Cossy at ESPCI Paris Tech found (Org. Lett. 2013, 15, 902) that the reagent XtalFluor-E (18) was effective for the coupling of N-Boc proline (17) and phenylglycine ethyl ester (19) without epimerization to furnish the dipeptide 20. The conversion of primary amide 21 to secondary amide 23 via cross-coupling with boronic acid 22 was reported (Org. Lett. 2013, 15, 2314) by Donald A. Watson at the University of Delaware. Catalysis of the Lossen rearrangement of hydroxamide 24 to carbamate 26 using N-methylimidazole (25), which helped to minimize side products, was reported (Org. Lett. 2013, 15, 602) by Scott J. Miller at Yale University. Keiji Maruoka at Kyoto University demonstrated (Angew. Chem. Int. Ed. 2013, 52, 5532) that propionaldehyde (27) could be converted under simple conditions to N-Boc aminal 28, which served as a convenient source for the in situ generation of the corresponding highly useful N-Boc imine.
Reactions of Alkenes
Authors: Lambert Tristan H.
Published: November 2020

Paul J. Chirik at Princeton University reported (Science 2012, 335, 567) an iron catalyst that hydrosilylates alkenes with anti-Markovnikov selectivity, as in the conversion of 1 to 2. A regioselective hydrocarbamoylation of terminal alkenes was developed (Chem. Lett. 2012, 41, 298) by Yoshiaki Nakao at Kyoto University and Tamejiro Hiyama at Chuo University, which allowed for the chemoselective conversion of diene 3 to amide 4. Gojko Lalic at the University of Washington reported (J. Am. Chem. Soc. 2012, 134, 6571) the conversion of terminal alkenes to tertiary amines, such as 5 to 6, with anti-Markovnikov selectivity by a sequence of hydroboration and copper-catalyzed amination. Related products such as 8 were prepared (Org. Lett. 2012, 14, 102) by Wenjun Wu at Northwest A&F University and Xumu Zhang at Rutgers via an isomerization-hydroaminomethylation of internal olefin 7. Seunghoon Shin at Hanyang University (experimental work) and Zhi-Xiang Yu at Peking University (computational work) reported (J. Am. Chem. Soc. 2012, 134, 208) that 9 could be directly converted to bicyclic lactone 11 with propiolic acid 10 using gold catalysis. A nickel/Lewis acid multicatalytic system was found (Angew. Chem. Int. Ed. 2012, 51, 5679) by the team of Professors Nakao and Hiyama to effect the addition of pyridones to alkenes, such as in the conversion of 12 to 13. Radical-based functionalization of alkenes using photoredox catalysis was developed (J. Am. Chem. Soc. 2012, 134, 8875) by Corey R.J. Stephenson at Boston University, an example of which was the addition of bromodiethyl malonate across alkene 14 to furnish 15. Samir Z. Zard at Ecole Polytechnique reported (Org. Lett. 2012, 14, 1020) that the reaction of xanthate 17 with terminal alkene 16 led to the product 18. The radical-based addition of nucleophiles including azide to alkenes with Markovnikov selectivity (cf. 19 to 20) was reported (Org. Lett. 2012, 14, 1428) by Dale L. Boger at Scripps La Jolla using an Fe(III)/NaBH4-based system. A remarkably efficient and selective catalyst 22 was found (J. Am. Chem. Soc. 2012, 134, 10357) by Douglas B. Grotjahn at San Diego State University for the single position isomerization of alkenes, which effected the transformation of 21 to 23 in only half an hour.
Advances in Alkene Metathesis: The Kobayashi Synthesis of (+)-TMC-151C
Authors: Taber Douglass F.
Published: November 2020

Shazia Zaman of the University of Canterbury and Andrew D. Abell of the University of Adelaide devised (Tetrahedron Lett. 2011, 52, 878) a polyethylene glycol-tagged Ru catalyst that is effective for alkene metathesis in aqueous mixtures, cyclizing 1 to 2. Bruce H. Lipshutz of the University of California, Santa Barbara developed (J. Org. Chem. 2011, 76, 4697, 5061) an alternative approach for aqueous methathesis, and also showed that CuI is an effective cocatalyst, converting 3 to 5. Christian Slugovc of the Graz University of Technology showed (Tetrahedron Lett. 2011, 52, 2560) that cross metathesis of the diene 6 with ethyl acrylate 7 could be carried out with very low catalyst loadings. Robert H. Grubbs of the California Institute of Technology designed (J. Am. Chem. Soc. 2011, 133, 7490) a Ru catalyst for the ethylenolysis of 9 to 10 and 11. Thomas R. Hoye of the University of Minnesota showed (Angew. Chem. Int. Ed. 2011, 50, 2141) that the allyl malonate linker of 12 was particularly effective in promoting relay ring-closing metathesis to 13. Amir H. Hoveyda of Boston College designed (Nature 2011, 471, 461) a Mo catalyst that mediated the cross metathesis of 14 with 15 to give 16 with high Z selectivity. Professor Grubbs designed (J. Am. Chem. Soc. 2011, 133, 8525) a Z selective Ru catalyst. Damian W. Young of the Broad Institute demonstrated (J. Am. Chem. Soc. 2011, 133, 9196) that ring closing metathesis of 17 followed by desilylation also led to the Z product, 18. Thomas E. Nielsen of the Technical University of Denmark devised (Angew. Chem. Int. Ed. 2011, 50, 5188) a Ru-mediated cascade process, effecting ring-closing metathesis of 19, followed by alkene migration to the enamide, and finally diastereoselective cyclization to 20. In the course of a total synthesis of (–)-goniomitine, Chisato Mukai of Kanazawa University showed (Org. Lett. 2011, 13, 1796) that even the very congested alkene of 22 smoothly participated in cross metathesis with 21 to give 23. En route to leustroducsin B, Jeffrey S. Johnson of the University of North Carolina protected (Org. Lett. 2011, 13, 3206) an otherwise incompatible terminal alkyne as its Co complex 24, allowing ring closing methathesis to 25.
C–O Ring Construction: The Georg Synthesis of Oximidine II
Authors: Taber Douglass F.
Published: November 2020

Chun-Bao Miao and Hai-Tao Yang of Changzhou University constructed (J. Org. Chem. 2011, 76, 9809) the oxetane 2 by exposing the Michael adduct 1 to I2 and air. Huanfeng Jiang of the South China University of Science and Technology carboxylated (Org. Lett. 2011, 13, 5520) the alkyne 3 in the presence of a nitrile to give the three-component coupled product 4. Alois Fürstner of the Max-Planck-Institut Mülheim cyclized (Angew. Chem. Int. Ed. 2011, 50, 7829) 5 with a Mo catalyst, released in situ from a stable precursor, to give 6 in high ee. Hiromichi Fujioka of Osaka University rearranged (Chem. Commun. 2011, 47, 9197) 7 to the cyclic aldehyde, largely as the less stable diastereomer 8. Edward A. Anderson of the University of Oxford cyclized (Angew. Chem. Int. Ed. 2011, 50, 11506) 9 to 10 with excellent stereochemical fidelity. Similarly, Michal Hocek of the Academy of Sciences of the Czech Republic, Andrei V. Malkov, now at Loughborough University, and Pavel Kocovsky of the University of Glasgow combined (J. Org. Chem. 2011, 76, 7781) the individual enantiomers of 11 and 12 to give 13 as single enantiomerically pure diastereomers. Daniel Romo of Texas A&M University cyclized (Angew. Chem. Int. Ed. 2011, 50, 7537) the bromo ester 14 to the lactone 15. Xin-Shan Ye of Peking University condensed (Synlett 2011, 2410) the sulfone 16 with 17 to give the sulfone 18, with high diastereocontrol. Jiyong Hong of Duke University found (Org. Lett. 2011, 13, 5816) that 19 could be cyclized to either diastereomer of 20 by judicious optimization of the reaction conditions. Stacey E. Brenner-Moyer of Brooklyn College showed (Org. Lett. 2011, 13, 6460) that cyclization of racemic 21 in the presence of 22 and the Hayashi catalyst delivered an ~1:1 mixture of 23 and 24, each with good stereocontrol. Kyoko Nakagawa-Goto of the University of North Carolina showed (Synlett 2011, 1413) that the MOM ether 25, prepared in high de by Evans alkylation, cyclized efficiently to 26. Armen Zakarian of the University of California Santa Barbara cyclized (Org. Lett. 2011, 13, 3636) 27, readily prepared in high ee by asymmetric Henry addition, to the enone 28.
C–N Ring Construction: The Harrity Synthesis of Quinolizidine (–)-217A
Authors: Taber Douglass F.
Published: November 2020

David M. Jenkins of the University of Tennessee devised (J. Am. Chem. Soc. 2011, 133, 19342) an iron catalyst for the aziridination of an alkene 1 with an aryl azide 2. Yoshiji Takemoto of Kyoto University cyclized (Org. Lett. 2011, 13, 6374) the prochiral oxime derivative 4 to the azirine 5 in high ee. Organometallics added to 5 syn to the pendant ester. Hyeung-geun Park of Seoul National University used (Adv. Synth. Catal. 2011, 353, 3313) a chiral phase transfer catalyst to effect the enantioselective alkylation of 6 to 7. Yian Shi of Colorado State University showed (Org. Lett. 2011, 13, 6350) that a chiral Brønsted acid mediated the enantioselective cyclization of 8 to 9. Mattie S.M. Timmer of Victoria University of Wellington and Bridget L. Stocker of Malaghan Institute of Medical Research effected (J. Org. Chem. 2011, 76, 9611) the oxidative cyclization of 10 to 11. They also showed (Tetrahedron Lett. 2011, 52, 4803, not illustrated) that the same cyclization worked well to construct piperidine derivatives. Jose L. Vicario of the Universidad del País Vasco extended (Adv. Synth. Catal. 2011, 353, 3307) organocatalysis to the condensation of 12 with 13 to give the pyrrolidine 14. Jinxing Ye of the East China University of Science and Technology used (Adv. Synth. Catal. 2011, 353, 343) the same Hayashi catalyst to condense 15 with 16 to give 17. André B. Charette of the Université de Montreal expanded (Org. Lett. 2011, 13, 3830) 18, prepared by Petasis-Mannich coupling followed by ring-closing metathesis, to the piperidine 20. Marco Bella of the “Sapienza” University of Roma effected (Org. Lett. 2011, 13, 4546) enantioselective addition of 22 to the prochiral 21 to give 23. Ying-Chun Chen of Sichuan University and Chun-An Fan of Lanzhou University cyclized (Adv. Synth. Catal. 2011, 353, 2721) 24 to 25 in high ee. Andreas Schmid of TU Dortmund showed (Adv. Synth. Catal. 2011, 353, 2501) that ω-laurolactam hydrolases could be used to cyclize the ester 26, but not the free acid, to the macrolactam 27.
Advances in Heterocyclic Aromatic Construction
Authors: Lambert Tristan H.
Published: November 2020

Rubén Vicente and Luis A. López at the University of Oviedo in Spain reported (Angew. Chem. Int. Ed. 2012, 51, 8063) the synthesis of cyclopropyl furan 2 from alkylidene 1 and styrene by way of a zinc carbene intermediate. The same substrate 1 was also converted (Angew. Chem. Int. Ed. 2012, 51, 12128) to furan 3 via catalysis with tetrahydrothiophene in the presence of benzoic acid by J. Stephen Clark at the University of Glasgow. Xue-Long Hou at the Shanghai Institute of Organic Chemistry discovered (Org. Lett. 2012, 14, 5756) that palladacycle 6 catalyzes the conversion of bicyclic alkene 4 and alkynone 5 to furan 7. A silver-mediated C–H/C–H functionalization strategy for the synthesis of furan 9 from alkyne 8 and ethyl acetoacetate was developed (J. Am. Chem. Soc. 2012, 134, 5766) by Aiwen Lei at Wuhan University. Ning Jiao at Peking University and East China Normal University found (Org. Lett. 2012, 14, 4926) that azide 10 and aldehyde 11 could be converted to either pyrrole 12 or 13 with complete regiocontrol by judicious choice of a metal catalyst. Meanwhile, Michael A. Kerr at the University of Western Ontario developed (Angew. Chem. Int. Ed. 2012, 51, 11088) a multicomponent synthesis of pyrrole 16 involving the merger of nitrone 14 and the donor–acceptor cyclopropane 15. The pyrrole 16 was subsequently converted to an intermediate in the synthesis of the cholesterol-lowering drug compound Lipitor. A robust synthesis of the ynone trifluoroboronate 17 was developed (Org. Lett. 2012, 14, 5354) by James D. Kirkham and Joseph P.A. Harrity at the University of Sheffield, which thus allowed for the ready production of trifluoroboronate-substituted pyrazole 18. An alternative pyrazole synthesis via oxidative closure of unsaturated hydrazine 19 to produce 20 was reported (Org. Lett. 2012, 14, 5030) by Yu Rao at Tsinghua University. A unique fluoropyrazole construction was developed (Angew. Chem. Int. Ed. 2012, 51, 12059) by Junji Ichikawa at the University of Tsukuba that involved nucleophilic substitution of two of the fluorides in 21 to form pyrazole 22.
The Reisman Synthesis of (+)-Salvileucalin B
Authors: Taber Douglass F.
Published: November 2020

Salvileucalin B 3 exhibits modest cytotoxicity against A549 (human lung adenocarcinoma) and HT-29 (human colon adenocarcinoma) cell lines. The compelling interest of 3 is its complex, highly functionalized heptacyclic skeleton. Sarah E. Reisman of the California Institute of Technology envisioned (J. Am. Chem. Soc. 2011, 133, 774) that the intramolecular cyclization of the diazo ketone 1 could offer an efficient entry to 2 and thus to 3. The key intermediate for the preparation of 1 was the acid 11. It was not possible to achieve communication between the two stereogenic centers of 11, so the decision was taken to establish these independently. This led to a strategy centered on the construction of the 1,2,3,4-tetrasubstituted aromatic ring. The absolute configuration of the stereogenic center of 8 was set by enantioselective addition of 5 to the commercial aldehyde 4. The absolute configuration of the second center was set using the Myers protocol. Although 10 could not be hydrolyzed without epimerization, cyclization followed by hydrolysis was effective, delivering 11 as a 10:1 mixture of diastereomers. From the algebra of mutual resolution, the major diastereomer, separated at a later stage, was of high enantiomeric purity. The acid 11 was homologated, first by the Arndt-Eistert procedure, then by condensation of the methyl ester so prepared with the anion of acetonitrile. Exposure of the derived diazo nitrile 1 to Cu catalysis under brief microwave irradiation led to smooth cyclization to the hexacyclic ketone 2. Although the skeleton of 2 was readily assembled, it is highly strained. This was made clear on Dibal reduction of the derived enol triflate. The product was clearly not the desired aldehyde 2, but rather 12, the product of Claisen rearrangement. Reasoning that the Claisen rearrangement is thermally reversible, and that the ether 12 would be stable to hydride, they carried forward with Dibal reduction—and were rewarded by the appearance of the desired primary alcohol from the reduction of 2. Pd-mediated cyclocarbonylation delivered 13, which was selectively oxidized to (+)-salvileucalin B 3.
The Kuwahara Synthesis of Paspalinine
Authors: Taber Douglass F.
Published: November 2020

The hexacyclic indole diterpenoid paspalinine 3, produced by the ergot Claviceps paspali, induces tremors in domestic animals that graze on pasture grass infected by that fungus. Shigefumi Kuwahara of Tohoku University envisioned (Angew. Chem. Int. Ed. 2012, 51, 12833) assembly of the tetracyclic nucleus of 3 by the oxidative cyclization of 1 to 2. The challenge, then, was the assembly of the angularly substituted trans–anti-trans-6-6-5 alicyclic nucleus of 1. The synthesis began with the Wieland-Miescher ketone 4, which is available commercially in enantiomerically pure form. Exposure to ethylene glycol under acidic conditions converted 4 to the known monoketal 5. The alkylation with 6 followed by selective hydrolysis gave 7 as an inconsequential mixture of diastereomers. Exposure to base effected both equilibration to the more stable equatorial diastereomer and cyclization to give the enone 8. There was still the problem of the introduction of the axial angular methyl group. This was solved by selective reduction of 8 to the endo alcohol. Hydroxyl-directed Simmons-Smith cyclopropanation followed by oxidation gave 9. The enolate resulting from the dissolving metal reduction of 9 was trapped with Comins reagent to generate the enol triflate 10. Acetanilide 11 was converted to the stannane 12 by ortho metalation following the literature protocol. Pd-mediated coupling of 12 with 10 proceeded efficiently to give 1. Oxidation with stoichiometric Pd trifluoroacetate then induced Type 5 indole formation (Tetrahedron 2011, 67, 7195). Hydrolysis and conjugation completed the synthesis of 2. To introduce the sidechain, the enone was converted to the allyl enol carbonate. Pd-mediated rearrangement converted that to the α-allyl enone, which participated in Ru-catalyzed metathesis with 14 to give 15. Asymmetric dihydroxylation proceeded with only modest diastereoselectivity, but only the desired diastereomer cyclized onto the ketone to give 16. The ketone 16 was an intermediate in Smith’s earlier synthesis. Professor Kuwahara devised an alternate end game, selenylation followed by oxidation and sigmatropic rearrangement, to install the axial OH and complete the synthesis of paspalinine 3.
Microbes and Minerals
Authors: Rickard David
Published: November 2020

Pyrite consists of two elements—iron and sulfur—but considerations of pyrite formation have mainly concerned sulfur. Iron is extremely abundant in the Earth; in fact, it is the fourth most abundant element on Earth and is less localized in its distribution. By contrast, sulfur is the 17th most abundant element in the Earth’s crust, and there are about 100 times more iron than sulfur. The interest in the primary role of sulfur in pyrite formation continues to the present day. In the Old Latin of early Republican Rome (i.e., before c. 200 BCE), sulfur was called sulpur or burning stone (i.e., brimstone). The p was pronounced with a puff of air. This puff was transliterated with an h following the p. When the f sound was introduced into classical Latin, p was often changed to ph in Latin words of Greek origin. Sulpur, however, had no Greek roots. The Greeks called it θείον (thion), which gave rise to our prefix, thio-. Sulfur had been written as sulphur in Old Latin, with the h indi­cating the puff of air after the p, but when the f sound was introduced this gave the mistaken impression that sulphur was originally a Greek word. At the end of classical times (around 27 BCE) the spelling was altered to sulfur, which is the spelling that usually appears in Latin dictionaries. In the last millennium, the element has traditionally been spelled sulphur in the United Kingdom and countries where UK rule held sway. By contrast, US English has continually used the correct sulfur spelling. The fountainhead of all chemical definitions worldwide, the International Union of Pure and Applied Chemistry, adopted the spelling sulfur in 1990. Finally, the UK authorities admitted their error and the UK Royal Society of Chemistry Nomenclature Committee recommended the correct spelling in 1992. In 2000 the authority determining quality and standards in UK schools decreed UK children should be taught the sulfur spelling. The sulphur spelling still occurs, but at best this is a literary affectation.
Acid Earth
Authors: Rickard David
Published: November 2020

The atmosphere and much of the rivers, lakes, and oceans of the Earth are oxygenated. Any pyrite that comes into contact with these environments becomes unstable and breaks down. The process is called oxidation. It is an exothermic process and, as described in Chapter 5, this process was thought to heat the Earth. It is the opposite of reduction, which we discussed with regard to the microbial formation of sulfide from sulfate in Chapter 6. The counterintuitive concept important here is that oxidation is a chemical process that does not necessarily need oxygen. This idea—that you can oxidize things in the absence of oxygen—is one that most natural scientists are aware of but that they need a couple of nudges occasionally to remind themselves about. This means that pyrite oxidizes not only in oxygenated environments—although that is what we are most familiar with—but also in oxygen-free environments. Among the products of pyrite oxidation are large quantities of acid. Although this happens naturally during rock weathering, the intervention of humankind has led to an enormous increase in the exposure of pyrite to the atmosphere. This has produced contamination of the atmosphere, groundwater, and watercourses on a regional scale. It has also increased the amount of uncontrolled coal burning in coal seams, coal mines, and coal waste tips worldwide, making whole towns uninhabitable and laying waste to large areas. In this chapter I consider in more detail what exactly the process of pyrite oxidation is and how it affects the Earth’s environment today, as well as the problems it stores up for humanity in the future. In chemical terms, oxidation does not mean just the addition of oxygen. Oxidation is a reaction that involves the removal of one or more electrons from a compound because of a chemical reaction. One of the most familiar oxidation reactions is combustion, where substances burn in air to produce heat. The way to put out such a fire is to restrict oxygen access using a chemical foam or fire blanket. Since this reaction with oxygen was the best known, the process was called originally called oxidation.
DDT Wars
Authors: Wurster Charles F.
Published: November 2020

DDT Wars is the untold inside story of the decade-long scientific, legal and strategic campaign that culminated in the national ban of the insecticide DDT in 1972. The widespread misinformation, disinformation and mythology of the DDT issue are corrected in this book. DDT contamination had become worldwide, concentrating up food chains and causing birds to lay thin-shelled eggs that broke in the nests. Populations of many species of predatory and fish-eating birds collapsed, including the American Bald Eagle, Osprey, Peregrine Falcon and Brown Pelican. Their numbers recovered spectacularly in the decades following the ban. During the campaign DDT and five other insecticides were found to cause cancer in laboratory tests, which led to bans of these six pesticides by international treaty in 2001. This campaign produced lasting changes in American pesticide policies. The legal precedents broke down the court "standing" barrier, forming the basis for the development of environmental law as we know it today. This case history represents one of the greatest environmental victories of recent decades. DDT is still "controversial" because it has been deceptively interjected into the "climate wars." This campaign was led by the Environmental Defense Fund (EDF), founded in 1967 by ten citizens, most of them scientists, volunteers without special political connections or financial resources. Their strategy was to take environmental problems to court. There were many setbacks along the way in this exciting and entertaining story. The group was often kicked out of court, but a few determined citizens made a large difference for environmental protection and public health. Author Charles Wurster was one of the leaders of the campaign. The first six years of EDF history are described as it struggled to survive. Now EDF is one of the world's great environmental advocacy organizations defending our climate, ecosystems, oceans and public health.
Escalating the DDT Issue with More Court Cases
Authors: Wurster Charles F.
Published: November 2020

While HEW and USDA pondered these appellate court decisions, we turned our attention to several more local DDT problems. From a New York Times article (May 3, 1970), we learned that the Olin Chemical Corporation was manufacturing about 20% of the nation’s DDT in buildings owned by the federal government and leased to Olin on the site of the U.S. Army’s Redstone Arsenal near Huntsville, Alabama. A DDT-contaminated effluent from this plant was leaking into the Wheeler National Wildlife Refuge at concentrations known to inhibit reproduction of birds and fish. The refuge also served as a drinking water supply for the city of Decatur, implying a human health hazard as well. Downriver fisherman were also eating their catch, thus concentrating DDT to higher levels as well. In October 1969, the federal Water Quality Administration had recommended a stricter pollution control standard for the Olin plant. Olin said it could not meet that standard, and the Army then overruled the Water Quality Administration’s recommendation. So on June 5, 1970, EDF, along with the National Audubon Society and the National Wildlife Federation, sued in Federal District Court against Olin, the Department of the Army, and the Corps of Engineers seeking to stop the DDT-contaminated discharge. The complaint was written by EDF’s new attorney, Edward Lee Rogers. I supplied the scientific support, which was easy, since it was similar, although steadily expanding, to the Wisconsin hearings and the USDA and HEW cases. Only three days later Olin threw in the towel! On June 8 Olin decided to close its DDT plant and no longer make DDT. DDT apparently was not worth defending. They said they had reached that decision shortly before our case was filed. True or not, it was a quick and easy victory. We needed it. We had won by winning. Even as the legal briefs went back and forth between EDF, USDA, HEW, and the appeals court, another DDT battle was brewing in California. For years scientists had been puzzled by the extremely high levels of DDT contamination along the coast of Southern California compared with other marine environments.
The Oxides of Nitrogen: Their Relation to Tropospheric Ozone
Authors: Calvert Jack G. , Orlando John J. , Stockwell William R. , Wallington Timothy J.
Published: November 2020

Reactive (or “odd”) nitrogen is emitted into the atmosphere in a variety of forms, with the most important being NOx (NO and NO2), ammonia (NH3), and nitrous oxide (N2O). Emissions of these species into the atmosphere have been summarized, for example, by the IPCC Fourth Assessment Report (the AR4; IPCC, 2007). Some discussion of NOx emissions and trends has also been presented in Chapter I. Emissions of NOx are mainly the result of anthropogenic activity associated with fossil fuel combustion and industrial activity. For the 1990s, the AR4 estimates total anthropogenic NOx emissions of 33.4 TgN yr−1, with natural emissions (mostly from soil and lightning) accounting for an additional 8.4–13.7 TgN yr−1. Ammonia emissions are comparable in magnitude to those for NOx, with anthropogenic emissions (45.5 TgN yr−1) again exceeding natural emissions (10.6 TgN yr−1). Although the majority of the ammonia produces aerosols or is scavenged by aerosol and is subsequently lost from the atmosphere, some gas phase oxidation does occur, which can in part lead to NOx production. The N2O source strength is about 17.7 TgN yr−1, with natural sources outweighing anthropogenic ones (IPCC, 2007). However, N2O is essentially inert in the troposphere, and thus the vast majority of its photooxidation and concomitant NOx release occurs in the stratosphere. The major NOx − related reactions occurring in the Earth’s troposphere are summarized in Figure III-A-1. As just alluded to, the species NO and NO2 are jointly referred to as NOx and are often treated collectively. This is because, under daytime conditions, these two species are rapidly interconverted, with the interconversion occurring on a much shorter timescale than the loss of either species.
The Impact of Inorganic Trace Gases on Ozone in the Atmosphere
Authors: Calvert Jack G. , Orlando John J. , Stockwell William R. , Wallington Timothy J.
Published: November 2020

A major focus of the previous six chapters has been on the chemistry and interactions of the HOx, NOx, and volatile organic compound (VOC) families. Details of the reactions of O3 NO3, and HO that act to initiate VOC oxidation have been presented, as has the ensuing chemistry involving organic peroxy and alkoxy radicals and their interactions with NOx. In this chapter, we complete our discussion of thermal chemical reactions that impact tropospheric ozone. The chapter begins with a discussion of the budgets of two simple (inorganic) carbon-containing species not yet discussed, carbon dioxide (CO2) and carbon monoxide (CO). Although CO2 is not directly involved in ozone-related tropospheric chemistry, it is of course the species most critical to discussions of global climate change, and thus a very brief overview of its concentrations, sources, and sinks is presented. CO is a ubiquitous global pollutant, and its reaction with HO is an essential part of the tropospheric background chemistry. This is followed by a presentation of the tropospheric chemistry of halogen species, beginning with a discussion of inorganic halogen cycles that impact (in particular) the ozone chemistry of the marine boundary layer (MBL) and concluding with a detailed presentation of the reactions of Cl atoms and Br atoms with VOC species. The chapter concludes with an overview of tropospheric sulfur chemistry. The reactions leading to the oxidation of inorganic (SO2 and SO3) as well as organic sulfur compounds (e.g., DMS, CH3SCH3) are detailed, and a brief discussion of the effects of the oxidation of sulfur species on aerosol production in the troposphere and stratosphere is also given. The abundance of CO2 in the atmosphere has obviously received a great deal of attention in recent decades due to the influence of this gas on Earth’s climate system. Indeed, changes in the atmospheric CO2 concentration represent the single largest contributor to changes in radiative forcing since preindustrial times (c. 1750). The atmospheric burden of CO2 is controlled by the processes that make up the global carbon cycle—the exchanges of carbon (mostly in the form of CO2) between various “reservoirs,” including the atmosphere, land (vegetation and soil), the surface ocean, the intermediate and deep ocean, sediment on the ocean floor, and the fossil fuel reservoir (IPCC, 2007).
Congress Misses the Mark
Authors: Revesz Richard , Lienke Jack
Published: November 2020

For polluters, America in 1970 was still something of a Wild West. A number of federal, state, and municipal laws aimed at improving air quality were already on the books, but few were enforced, and pollution from the nation’s ever-growing stock of motor vehicles, power plants, and factories remained uncontrolled in much of the country. A passage from the Ralph Nader Study Group’s Vanishing Air, published in May 1970, vividly illustrates the extent to which dirty air was a fact of life for city dwellers of the period: . . . The New Yorker almost always senses a slight discomfort in breathing, especially in midtown; he knows that his cleaning bills are higher than they would be in the country; he periodically runs his handkerchief across his face and notes the fine black soot that has fallen on him; and he often feels the air pressing against him with almost as much weight as the bodies in the crowds he weaves through daily. . . . New York’s problems with air quality were hardly unique. In an October 1969 letter to the Senate Subcommittee on Air and Water Pollution, a resident of St. Louis expressed similar sentiments about the sheer pervasiveness of pollution in her community: . . . What really made me take the time to write this letter was the realization that I had begun to take the haze and various odors for granted. Close the doors and windows and they’ll be less noticeable[. I]t is very disturbing to think I’ve become used to the burning-rubber smell in the evening and the slightly sour smell in the morning. What does air smell like? . . . And air pollution’s costs went far beyond sour smells and dirty handkerchiefs, as a series of deadly “inversions” both here and abroad had made dramatically clear beginning in the late 1940s. Typically, the air at higher altitudes is cooler than that below. This is because the surface of the earth absorbs sunlight and radiates heat, warming the air closest to the ground. That warm surface air then cools as it rises higher into the atmosphere.
Using Smart Environment Technologies to Monitor and Assess Everyday Functioning and Deliver Real-Time Intervention
Authors: Schmitter-Edgecombe Maureen , Cook Diane J.
Published: November 2020

Technology is changing healthcare and our understanding of human behavior. To date, most of our theories about behavior, everyday activities, and cognitive health have been formed based on questionnaire data, laboratory tests and experiments, and placing observers within the environment to record human behavioral habits. Smart technologies offer an opportunity to passively collect data about human behavior within the everyday environment. The possibilities for using smart technologies that can adapt, sense, infer, learn, anticipate, and intervene for health monitoring and intervention are considered “extraordinary” (Department of Health, 2007). Our Smart Home group affiliated with the Center for Advanced Studies in Adaptive Systems (CASAS) and others have been studying the role of smart environments as a type of “cognitive prosthesis” in which the smart environment operates alongside humans in order to monitor, maintain, and enhance their health and functional capabilities and overcome their limitations. For the clinical neuropsychologist, smart environment technologies offer opportunities for new methods of data collection, for both clinical and research purposes. Over the past decade, people perform their normal activities of daily living. The data can then be used to support everyday activities and to assist in rehabilitation and proactive interventions through real-time assistance and monitoring of real-world responses to intervention. The data can also be used to improve our understanding of the effects of cognitive impairment on everyday functioning as well as theories about behavior. The chapter begins with a discussion of research in the sensor technologies have become more mature. For example, sensor power and capacity have increased while sensor size and cost have decreased. Similarly, there has been significant progress in the areas of wireless networks, data processing, and machine learning. Data can now be automatically collected from sensor-filled smart homes (environmental or fixed devices), activity trackers (wearable devices), and smartphones (portable devices) in an unobtrusive manner while area of activity recognition, followed by application of this work to functional and health assessment and to activity-aware intervention.
Strangled Waters: First Wave
Authors: Levy Sharon
Published: November 2020

On a balmy day in June 1955, George Anderson took his sailboat out on Lake Washington, the long stretch of fresh water that separates Seattle from its eastern suburbs. Anderson had recently finished his doctoral research on phytoplankton, and knew the lake well. The water that day looked odd; he noticed a strange brown tinge. So he collected a sample in an empty beer bottle and brought it back to the University of Washington lab where he worked with his mentor, W.T. Edmondson, the ranking authority on the lake. Under the microscope, Anderson and Edmondson found a life form they’d never seen before. It grew in long, narrow chains, striated with lines that separated one cell from the next. They thought this might be a species infamous among limnologists, the cyanobacterium Oscillatoria rubescens. (Cyanobacteria, popularly known as blue-green algae, are in fact distinct from and far more ancient than algae. They appeared more than 3 billion years ago, when the planet was inhabited only by microbes, and were the first organisms to evolve photosynthesis. Their proliferation and release of great volumes of oxygen profoundly changed the chemical makeup of Earth’s atmosphere, making the evolution of complex life possible.) The researchers needed to be sure, so they sent a sample off to an expert, who confirmed their suspicions. O. rubescens signaled deteriorating conditions in Lake Washington. To Edmondson, it also meant an unprecedented opportunity to track the impacts of nutrient overload. O. rubescens had been the harbinger of drastic change in a number of western European lakes. The best-known case was that of Lake Zurich in Switzerland. Fed by Alpine glaciers, Lake Zurich was, until the late 1800s, an expanse of blue known for its abundant populations of whitefish and lake trout, which thrive in deep water. The lake is made up of two basins separated by a narrow passage. In the late nineteenth century towns at the edge of the lower basin, the Untersee, abandoned privies for flush toilets, and began to release their raw sewage into the lake.
Do- It- Yourself Wetlands
Authors: Levy Sharon
Published: November 2020

Bob Gearheart emerged as Arcata’s marsh guru during the city’s long battle with the state water bureaucracy. This unpaid post demanded that Gearheart crank out proposals for wetland treatment at a frenetic pace, knowing that the city’s financial future depended on his work. He wore a smile, energized by the pressure. Gearheart’s son, Greg, grew up to become an environmental engineer working for the state water board. He earned his engineering degree at Humboldt State, studying with his father. He remembers his dad happily engaged during the battle for Arcata’s alternative treatment system, at the same time he was teaching a full load of classes. “My dad likes a fight,” Greg says. “He adapts well. People put an obstacle in front of him, and he figures out a way to make it look like it’s not really a problem. He makes it look like it was stupid on his opponent’s part to put the obstacle there.” In 1977, the elder Gearheart proposed a first: a wetland built to treat municipal wastewater to the standards required under the Clean Water Act. He possessed a serene certainty that he could make this untried system work. “I had no data until we did the pilot study,” he remembers, “but I was one hundred percent confident.” The power of aquatic plants to cleanse polluted water had first been tested in the 1950s by Käthe Seidel, a researcher at the Max Planck Institute in Germany. She showed that while some wild plants were killed off by waters tainted with phenol—a toxic organic compound used in making plastics—others had a remarkable ability to adapt. At first contact, effluent containing phenol caused bul­rush stems to wither away, but the roots survived and in time sent up healthy new shoots. Bulrush, it turned out, could break down phenol, metabolizing it into the amino acids that build protein. The plant also thrived in domestic sewage. Seidel used carefully groomed cultures of wetland plants, rooted in beds of gravel or sand through which effluent flowed.
Of Time and the Wetland
Authors: Levy Sharon
Published: November 2020

At the oldest of Arcata’s treatment wetlands, it’s now possible to walk on water. Over three decades of filtering sewage, Arcata’s wetland cells have developed floating mats of dead cattail stems and leaves underlain by living roots, resilient enough to support a person’s weight. The short journey across Treatment Wetland 3 is a strange experience, like walking on a soggy trampoline. Water seeps through the cattail mat and into footprints. On a February day, a dense maze of brown cattail stems stretches twelve feet above the wetland’s surface, their shaggy brown seedheads waving in the breeze. A stroll across the treatment wetland is as close as a modern American can hope to get to the feel of the floating tule islands that William Finley camped on in the upper Klamath Basin in 1905, and that crowded California’s unspoiled marshes before the Gold Rush. The floating mats in Arcata were created by accident when the city’s treatment plant operators increased the depth of the treatment marshes, part of an effort to improve their declining performance. To their surprise, the dense growth of cattail rose off the bottom and continued to thrive, roots dangling in the water. The wetlands have aged. “Arcata’s is the grandmother municipal treatment wetland,” says David Austin, an environmental engineer with CH2M Hill who specializes in treatment wetlands design. Austin remembers studying the Arcata wetlands as a student at University of California at Davis in the 1990s. “It was a pioneering system. Now it’s an old design— one that wouldn’t be used today.” In 2016, three decades after Bob Gearheart’s unconventional marshes began cleaning Arcata’s sewage, the city’s wastewater plant faced a crisis. During the cold rains of winter, the system often failed to perform to the standards set in its discharge permit. Every part of the plant had aged to the point where its performance was in decline. At the headworks, the two giant Archimedes screws that push raw sewage uphill through a coarse screen had been running for decades; their metal housings were rusting away.
The Fight This Time
Authors: Levy Sharon
Published: November 2020

Forty- five years after the passage of the Clean Water Act (CWA), water pollution remains a profound problem. More than forty- seven thousand US waters are impaired. At the rate these lakes, rivers, and estuaries are being cleaned up, it will take more than five hundred years to make them all safe for swimming and fishing. Oliver Houck, a professor of law at Tulane University who has focused on environmental protection since the 1970s, sums up the situation: “We have not had clean water in America,” he writes, “in the lifetime of anyone living.” The major source of pollution in the waters of the US, as in other developed countries, is now runoff from farm fields and city streets. These nonpoint sources remain difficult to control. More than 75 percent of the rivers and lakes that fail to meet water quality standards are tainted by nonpoint sources. In terms of nutrient pollution, agricultural runoff is by far the dominant source, triggering harmful algal blooms from Chesapeake Bay to Puget Sound. The CWA of 1972 addressed point sources of pollution in a decisive and radical way. Section 402 of the CWA applies effluent standards based on the best available treatment technology to city sewage and industrial wastewaters, and puts regulatory power in the hands of the federal Environmental Protection Agency (EPA). Regulation under this scheme has brought dramatic improvement in water quality. Before the CWA was enacted, major urban river systems throughout the country had such low levels of dissolved oxygen that fish kills became routine, and urban beaches were often closed due to fecal contamination. By the late 1990s, dissolved oxygen levels had improved in about 70 percent of river reaches and watersheds studied by the EPA, and fish had returned to many waters. Beach closures decreased. Problems remain, especially in cities like Chicago and Baltimore, where heavy rains can overwhelm treatment systems, releasing raw sewage downstream. Still, in terms of curbing point source pollution, the CWA has made a critical difference. The rise of pollution from unregulated nonpoint sources has eaten away at these water quality gains. The Mississippi River basin, whose waters flow into the northern Gulf of Mexico, may be the most dramatic example. In August 2017, the Gulf’s dead zone grew to an unprecedented 8,776 square miles, about the size of New Jersey.
A Mother’s Perspective on Autism
Authors: Ellis Michael
Published: November 2020

From the moment you discover that you are going to be a parent, the hopes, dreams, and expectations you have for your­self and your child flood your mind. No matter how your child is to arrive, your heart is full of hope and promise. You begin to let yourself plan your future. Will your child become president, a doctor, a lawyer, work in the family business, or win the Nobel Peace Prize? Will he or she possess a special talent or skill? Your mind wanders and daydreams of all that is to come. The moment they place your beautiful child in your arms, you realize that there is no greater feeling. You are in love. There is no feeling deeper or grander. The unimaginable joy and gratitude for the blessing of your child is overwhelming. We all know those moments where your heart surged out of your body in awe of the blessing you were given. You may have even asked yourself, “How did I get so lucky?” I can relate. The moment they placed my daughter in my arms for the first time, I knew I had a greater purpose. I would not find out how much for another two years. I devoted myself to her; her care, her introduction to the world, and to the very amazing person I knew she would become. I gave everything of myself tirelessly to her. Her every whimper, cry, or gesture was met with a response. I could anticipate her needs and wants before she fully expressed them. I thought I had an undeniable bond with my daughter. I did. I had a bond that needed no words. That was the problem: we did not need words. If you are like me, you noticed at first subtle differences in your child, and then later there were glaring and alarming indications something was not developing correctly. But, no matter your education or your intelligence level, denial can be a powerful thing.
Non-Medication Therapies for ASD
Authors: Ellis Michael
Published: November 2020

There are a multitude of nonpharmacological (non-medication) therapies for autism spectrum disorder (ASD). These therapies generally have mainstream acceptance, especially compared with the complementary and alternative medicine (CAM) treatments mentioned in Chapter 7. Unfortunately, some of these non-medication therapies have little scientific evidence to support their effectiveness. Even those therapies that have some proven efficacy, and likely do work, are based on low-quality studies. Much more research is needed to prove that these therapies improve the symptoms of ASD and associated symptoms, and further studies are needed to differentiate in which children these therapies work best, the necessary treatment frequency and duration, and how young to begin these therapies. It is paramount that you be vigilant in researching and choosing the best therapy for your child. Many people are more than happy to take your money, and they know that you are vulnerable. Although many of these non-medication therapies are far from dangerous, wasting your time and money on the wrong therapy is harmful to your child and your family. The younger your child starts therapy or interventions, the greater the improvement is likely to be and the larger the impact on your child’s future. Thus, if you waste this window of opportunity on the wrong treatment, you will harm your child’s future. Luckily, there is sound evidence to support some of the therapies we will discuss. Applied Behavioral Analysis (ABA), as well as the behavioral interventions in general, has the best evidence to support its use in improving ASD symptoms in your child. Behavioral interventions for ASD are the most available and utilized category of nonpharmacological therapies as they are based on learning principles that are quite logical and evidence-based. One of the most widely recognized behavioral interventions/therapies is ABA, a type of therapy that uses learning and behavior techniques and principles to bring about positive changes in behavior. ABA is effective when applied to academics, adaptive skills, social skills, vocational skills, and communication. The goal of ABA therapy is to increase new skills and decrease problem behaviors.