CONTAMINANTES ORGANICOS PERSISTENTES EN FAUNA SILVESTRE: PERSPECTIVA LATINOAMERICANA. Miguel A. Mora, Ph.D. Professor Texas A&M University

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CONTAMINANTES ORGANICOS PERSISTENTES EN FAUNA SILVESTRE: PERSPECTIVA LATINOAMERICANA Miguel A. Mora, Ph.D. Professor Texas A&M University

Birds as Indicator Species Top of the food chain Photo: The Peregrine Fund Audubon.org Aquatic Environments Fish diets http://animals.nationalgeographic.com/animals/birds/bald-eagle/

Organochlorine Pesticides Hydrocarbons with chlorines inserted in place of H atoms. Designed as poisons. Tend to be lipid soluble & potentially biomagnify H 3 C H 3 C H 2 C x H 3 C H O C O CH 3 C 1,2,3,4,5,6-Hexachloro-cyclohexane Lindane Toxaphene Methoxychlor O Chlordane Aldrin Dieldrin/Endrin

Agricultural pesticide use

Polychlorinated biphenyls (PCB) Used as lubricants, heat conductors in electrical transformers, and plasticizers Toxic and can biomagnify because they only slowly degrade in the environment and they are very soluble in lipids 4' 3' 2' 1' 1 2 3 4 5' 6' 6 5 Biphenyl 2,3,5,3',5'-Pentachloro-biphenyl (PCB)

Chlorinated Phenols OH OH 2,4,5-Trichlorophenol (TCP) 2,3,4,5,6-Pentachlorophenol (PCP) Are produced during some processes such as papermill processing and Kraft bleaching of wood pulp Used as wood preservatives, biocides, and fungicides.

Polychlorinated dibenzodioxins (PCDD) & dibenzofurans (PCDFs) Created as byproducts in chemical production Dioxins in Agent Orange of Vietnam War Era Created during combustion and Kraft process Very persistent 8 9 O 1 2 O 7 3 O O O 6 4 Dibenzo-p-dioxin 2,3,7,8-Tetrachloro-dibenzo-p-dioxin 2,3,7,8-Tetrachloro-dibenzofuran

Brominated Flame Retardants Applied to combustible materials Plastic, Wood, Paper, Textiles, Cars, Computers Material can be either covalently bound or just blended into product Blended materials are more likely to leach into the environment

Perfluorocarbon structures. The general structures of (a) sulfonated perfluorochemicals (x=4 10, Y=OH, OM +, or NH 2 ) and (b) perfluorooctane-sulfonylfluoride (POSF) are shown. Surfactants Carpets Leather paper Upholstery Fabric Packaging Giesy and Kannan 2002, Environ. Sci. Technol. 146A-152A

DES - pharmaceutical Bisphenol A - plasticizer o,p DDT - Pesticide Well known endocrine disruptors E 2 4-nonylphenol - surfactant PCBs - industrial chemical Kepone - pesticide

Dioxins/Furans & Great Lake Cormorants As An Example AH receptor-mediated mechanism of action manifests in many ways - reproductive failure - teratogenic (including brain) - edema in chicks - endocrine disruption - cancers Also FWS concern with mid-atlantic peregrine falcons Also general concern about fish-eating birds. Sum AH receptor-mediated toxicants (dioxins,furans, some PCBs) using TEF to express as sum of TCDD equivalents ( TEQs)

A pod of orcas in the northern fjords of Norway. PCBs remain a major threat to marine apex predators such as orcas Persistent pollutants, persistent threats Paul D. Jepson, and Robin J. Law Science 2016;352:1388-1389 Published by AAAS

State parties to the Stockholm Convention as of May 2009. PCBs Endrin Dioxins Chlordane Furans HCB Aldrin Mirex Dieldrin Toxaphene DDT Heptachlor The Dirty Dozen Adopted in 2001, entered into force in 2004

State parties to the Stockholm Convention as of May 2009. α,β, γ-hch Tetra, Penta, Hexa, Hepta bromodiphenyl ethers Pentachlorobenzene Perfluorooctane sulfonic acid Perfluorooctane sulfonil fluorides 9 New POPs added to Annex A Adopted in 2001, entered into force in 2004

H H C C C C p,p' DDT H p,p' DDD Photo: The Peregrine Fund C. DDT banned in the USA in 1972. Banned in Canada in 1975. In Mexico Not used in agriculture since about 1978 Used for malaria control until about 2000 C p,p' DDE

Some effects of DDE on wildlife Eggshell thinning Antiandrogenic Skewed sex ratios Decreased thyroxine levels in plasma Reduced embryonic viability Hypothyroidism Enlarged liver, abnormal weights

Box 9.1 Pesticides and raptors: sentinel species warn of danger (2)

SEMARNAT, 2003

Tropical ecotoxicology: Status and needs 1997 Tropical ecosystems contain @ 75% of the global biodiversity Threatened by population growth, habitat degradation, deforestation, agricultural expansion Little research on ecotoxicology; most on water quality and aquatic ecotoxicology Lacher et al. 1997

DDE accumulation in migrant birds. No differences between summer and winter or fall and spring. Increase towards the north, U.S.-Mexico border

Where has all the DDE Gone? Searching for hotspots and patterns of accumulation in migrant Birds in North America

http://www.arctic.uoguelph.ca/cpe/arcticnews/articles/grasshopper/grasshopper.htm The Grasshopper Effect

DDE database for North American birds, 1980-2009 Data N Studies 272 Samples analyzed 16,594 Mean values 2,853 Locations 737 Geographic distribution Isla Isabel, Mexico Seymour Island, Canada Species 204 Orders 15

p,p -DDE in eggs of piscivorous birds in North America 1980-2009 West Central East

DDE in Passerine Birds from North America p,p'-dde, ( g/g ww) 35 30 25 20 15 10 5 0-5 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 Latitude

DONATE Subscribe to our eletter Go Search our news archives Songbirds dying from DDT in Michigan yards; Superfund site blamed ShareThis July 28, 2014 http://www.environmentalhealthnews.org/ehs/news/2014/jul/deadrobins American Robin Convention By Brian Bienkowski Staff Writer Environmental Health News July 28, 2014 ST. LOUIS, Mich. Jim Hall was mowing the town s baseball diamond when he felt a little bump underneath him. And there it was, a dead robin, he said.

POPs in Latin America Great lack of research on levels of POPs in Latin America (Allsopp 2000) Several POP studies with birds in Mexico, one in Chile, none for rest of LA (Allsopp 2000) Majority of research on POPs in wildlife have been in Mexico and Brazil. Data limited to levels of a few OC pesticides (Albores et al. 2000)

Wildlife toxicology studies in Mexico, 1997-2015 (not including metals) Number of publications Birds (18): swallows, falcons, songbirds, osprey, marine birds, aquatic birds Amphibians (3): turtles and lizzards Mammals (2): wild rodents, otters other Most or all studies on pesticides or persistent organic pollutants, none on PBDEs or PFOS

Wildlife contaminant studies in Central America (1997-2015) Costa Rica Birds (13)- neotropical migrant and resident passerines Amphibians and reptiles (15): frogs, turtles, caiman, crocodile Mammals (2): sloths, mice Buff-breasted Sandpiper Other CA Countries (0)

Wildlife contaminant studies in South America (1997-2015) Brazil: 3, birds, honey, general Argentina: 14 amphibians and reptiles Penguins General Chile: 0 Colombia (3): Amphibians and birds Venezuela: 0 Ecuador: 1, Oil Buff-breasted Sandpiper

Some observations: Research on dioxins, PBDEs, PFOS, and COPECs are very limited to a few wildlife studies (Albores et al. 2000)

Concentrations of 2,3,7,8- substituted PCDDs and PCDFs in air in the GRULAC region (femtograms of TEQ per cubic meter of air) Schuster et al 2015

Background ΣBDE concentrations (μg kg 1 lw)measured in tissues (liver, eggs) of birds inhabiting freshwater ecosystems Standard text and graphics

Mean PBDE concentracions in migrant and resident songbirds from Texas, Mexico and Costa Rica, 2012-2013 Data from A. Maldonado, PhD Student, Texas A&M University

PFOS in fish and wildlife

Giesy and Kannan 2001

Global distribution of PFASs in the tropical and subtropical oceans Gonzalez -Gaya et al. 2014

PFOS studies Dolphins in Brazilian Coast (Dorneles et al 2008) Dolphins also used for PCB studies in Brazil and Argentina One study with birds

PFAAs, PFOS, PFCAs Data from southern hemisphere lacking, particularly from South America Poor Coverage from tropical areas Limited work on terrestrial ecosystems Reiner and Place 2015

Conclusions after 20 years Studies are still scarce Pesticides are still of most concern Focus is still the individual slight link to population Impacts on populations mostly unknown