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Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

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Evaluating threats to humans and aquatic ecosystems posed by agriculture around the Rio Sierpe, Costa Rica Evaluar las amenazas representada para los seres humanos y los ecosistemas acuáticos por la agricultura en el Río Sierpe, Costa Rica Willy Eldridge, Dave Arscott, and Bern Sweeney SWRC Report 2012009 Final Report submitted to the Blue Moon Fund Grant 32023 11 December 2012
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Page 1: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

Evaluating threats to humans and aquatic

ecosystems posed by agriculture around the

Rio Sierpe, Costa Rica

Evaluar las amenazas representada para los seres humanos y los ecosistemas

acuáticos por la agricultura en el Río Sierpe, Costa Rica

Willy Eldridge, Dave Arscott, and Bern Sweeney

SWRC Report 2012009

Final Report

submitted to the

Blue Moon Fund

Grant 32023

11 December 2012

Page 2: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

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I. SUMMARY

We determined that food fish in a tributary to the Rio Grande de Térraba near the town of

Puerto Cortez and in the Estero Azul on the Rio Sierpe are contaminated with pesticide

residues that could threaten consumers. In the U.S.A., the observed concentrations would

lead to restricted consumption advisories for machaca (machaca or sabalo, Brycon behreae,

0.7-1.1 meals per month), tilapia (tilapia, Oreochromis niloticus, 3.6 meals per month) and

robalo aleta manchada (blackfin snook, Centropomus medius, 6.5 meals per month) for fish

caught in these two locations. Other species such as pargo (snapper, Lutjanus sp.), bagre (sea

catfish, Cathorops sp.), camarones de aqua dulce (freshwater shrimp, Palaemonetes sp.), and

piangua (cockles, Anadara tuberculosa) from elsewhere in the Humedal Nacional Térraba-

Sierpe (HNTS), the freshwater portion of the Rio Sierpe or lower Rio Térraba, or from the

ocean near the Rio Sierpe are safe to eat in unlimited quantities (i.e., >16 meals per month).

These recommendations are based upon 227 g (0.5 lb) of skin-on fish filet, whole clam or

whole shrimp per meal and apply to a 70 kg (154 lbs) person. Cleaning or cooking which

reduces the fat content, where most of the pesticides are stored, may reduce the risk to

consumers, whereas consuming the head or organs may increase the risk to consumers. Other

routes of exposure such as water, soil, other foods, or occupational exposure, may increase

the risk to consumers.

The concentrations of 63 organochlorine, organophospate, pyrethroid and trazine pesticides

or their breakdown products were measured in 41 fish and shellfish samples representing 7

species of fish, 1 species of mollusc and 1 species of crustacean from 19 sites throughout the

HNTS, Rio Sierpe, lower Rio Grande de Térraba and ocean off of the Rio Sierpe collected in

August and November 2011. A subset of 29 organochlorines and their derivatives were

measured in 4 additional shellfish samples. All samples contained detectable levels of at least

1 or as many as 25 chemicals and a total of 34 chemicals were detected across all fish and

shellfish representing 20 pesticides. The pesticides that pose the biggest threat to humans

tended to be organochlorine pesticides that have been prohibited in Costa Rica for decades

such as Dieldrin and DDT. The concentrations detected in fish filets suggest that no new

application has occurred since the bans were put in place a few decades ago, but rather

current concentrations reflect the persistent and bioaccumulative nature of these chemicals.

Chlorpyrifos, a pesticide whose use in Costa Rica is permitted with restrictions, was also

detected at concentrations that could be a concern. Other current use pesticides were

occasionally detected in high quantities in fish sampled within or near rice farms, but these

did not reach concentrations thought to pose a health risk to human consumers.

Of the three major forms of agriculture in the area, rice farming is a likely source for new

contaminants. Although farmers have shifted towards pesticides that breakdown or leave the

system quickly or pose a low health risk to consumers, some of the pesticides in use are

extremely toxic to fish and aquatic invertebrates in small doses. Two fish kills were noted

downstream from rice farms in the HNTS in 2011 following aerial application of pesticides.

The threats to humans from pesticide application may be shifting from a risk to human health

caused by ingesting contaminated fish to a threat to the food supply due to reduced

abundance and biomass of food fish.

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Future research should focus on collecting additional information on fish harvest and

consumption to more accurately evaluate threats from eating contaminated fish, and

determining the status of food fish stocks caught by small scale commercial and artisanal

fisherman in southwestern Costa Rica.

RESUMEN

Se determinó que el pescado atrapado en un afluente del Río Grande de Térraba, cerca de la

ciudad de Puerto Cortez, y en el Estero Azul del Río Sierpe, estaba contaminado con residuos

de plaguicidas que pueden ser peligrosos para los consumidores. En los Estados Unidos, las

concentraciones observadas habrían generado recomendaciones de restricción del consumo

de pescado atrapado en esos dos sitios: para la machaca o sábalo (Brycon behrea) a 0.7-1.1

veces (comidas) por mes; la tilapia (Oreochromis niloticus) a 3.6 veces por mes; y el róbalo

aleta manchada (Centropomus medius) a 6.5 veces por mes. Otras especies, como el pargo

(Lutjanus sp.), el bagre (Cathorops sp.), los camarones de agua dulce (Palaemonetes sp.) y la

piangüa (Anadara tuberculosa), pescadas en otras áreas del Humedal Nacional de Térraba-

Sierpe (HNTS), las porciones de agua dulce del Río Sierpe y los bajos del Río Térraba, así

como en el mar cerca de la boca del Río Sierpe, son perfectamente aptas para el consumo en

cantidades ilimitadas (es decir, más de 16 comidas por mes). Estas recomendaciones se basan

en porciones de 227g (media libra) de filete de pescado con piel, de almeja entera o de

camarón entero por comida y se aplican a personas de unos 70 Kg. (154 libras). Limpiar o

cocinar el pescado, lo que reduce el contenido de grasa que es donde se acumulan los

pesticidas, puede reducir el riesgo para los consumidores, mientras que consumir la cabeza o

los órganos puede aumentar el riesgo. Otras fuentes de exposición, tales como el agua, el

suelo, otras comidas o exposición laboral a los pesticidas, puede aumentar el riesgo para los

consumidores.

Se midió la concentración de 63 pesticidas organoclorados, organofosfatados, piretoides y de

trazina, así como de sus productos de descomposición, en 41 muestras de pescados y

mariscos, que representan 7 especies de peces, 1 especie de molusco y 1 especie de crustáceo

recolectados en 19 sitios del HNTS, el Río Sierpe, los bajos del Río Grande de Térraba y el

océano en la boca del Río Sierpe entre agosto y noviembre del 2011. Se midió también la

concentración de un subconjunto de 29 organoclorados y sus derivados en 4 muestras

adicionales de mariscos. Todas las muestras contenían niveles detectables de al menos 1 y de

hasta 25 sustancias químicas, y se detectó un total de 34 productos químicos, representando

20 plaguicidas, entre todos los pescados y mariscos analizados. Los plaguicidas que

representan mayor peligro para los seres humanos tienden a ser organoclorados que están

prohibidos en Costa Rica desde hace décadas, como la Dieldrina y el DDT. Las

concentraciones detectadas en los filetes de pescado sugieren que no es que se ha vuelto a

aplicar estas sustancias desde la prohibición hace varias décadas, sino que las

concentraciones actuales reflejan la naturaleza persistente y bioacumulativa de estas

sustancias químicas. También se detectaron concentraciones de Chlorpyrifos, un pesticida de

uso restringido en Costa Rica, en cantidades que podrían resultar preocupantes. Se detectó la

presencia de otros plaguicidas de uso común en altas concentraciones en muestras de pescado

obtenidas dentro o en las cercanías de fincas arroceras, pero no llegaron a tener

concentraciones que puedan representar un riesgo para la salud de los consumidores

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humanos.

De las tres actividades agrícolas principales de la zona, la producción arrocera es una fuente

potencial de nuevos contaminantes. Aunque cada vez los agricultores utilizan más

plaguicidas que se descomponen o abandonan el sistema rápidamente, o que representan un

riesgo muy bajo para la salud de los consumidores, algunos de los productos utilizados son

extremadamente tóxicos en pequeñas dosis para los peces y los invertebrados acuáticos. En el

2011, dos muertes de peces fueron anotadas en el HNTS, río abajo de fincas arroceras,

después de una aplicación aérea de plaguicidas. El peligro a la salud humana en relación con

el uso de plaguicidas parece estar pasando de un riesgo debido al consumo de pescado

contaminado, a una amenaza a la disponibilidad de alimentos, producto de la reducción de

abundancia y biomasa de pescado.

Las futuras investigaciones deberían enfocarse en recopilar información adicional sobre la

pesca y el consumo de pescado, para poder evaluar con mayor precisión las amenazas

generadas por el consumo de pescado contaminado, y determinar el estado de las reservas de

pescado capturado por pescadores comerciales y artesanales de pequeña escala en el suroeste

de Costa Rica

II. HAVE THE GOALS AND OBJECTIVES CHANGED? HOW?

The goal and objectives of the project have not changed. The goal of the project was to evaluate

the threats to humans posed by agriculture around the Rio Sierpe, Costa Rica. To achive this goal

we addressed the following objectives:

1. Develop an understanding of agricultural activities within the Rio Sierpe and lower Rio

Grande de Térraba watersheds

2. Identify and sample food fish and shellfish species

3. Evaluate variation in pesticide residue concentrations within and among fish and shellfish

species and sites

4. Evaluate risk to consumers from eating contaminated food fish and shellfish.

5. Develop an understanding of water physiochemistry

III. ACCOMPLISHMENTS

Study area: The project was conducted in the vicinity of the Humedal Nacional Térraba-

Sierpe (HNTS) in the Osa Province, Costa Rica. The study area included the lower Rio

Grande de Térraba where the Rainforest Alliance has established connections with rice

farmers, as well as the freshwater portions of the Rio Sierpe where we had previously

conducted a project for the Blue Moon Fund.

Objectives, Methods, and Results

1. Develop an understanding of agricultural activities within the Rio Sierpe and lower

Rio Grande de Térraba watersheds

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We initiated a literature review, discussions with the Rainforest Alliance, and

discussions with local land-owners, farmers, fisherman, guides, and performed

ground truthing to develop an understanding of land use within the Rio Sierpe and

Rio Térraba watersheds.

The ECOTICOS group created GIS maps of existing land use including a time

series of maps depicting how land use has changed over time in the Rio Sierpe

and lower Rio Térraba watersheds. Bananas were the dominant crop within the

Rio Sierpe and Rio Térraba watersheds until the 1970’s. Current agriculture

includes rice, palm oil, bananas, teak, and grazing. We used GIS information

from the ECOTICOS group to create a map of rice farms, other agriculture and

mangrove/wetlands in the region (Figure 1).

a. Size and location of rice paddies

Rice, of the species Oryza sativa, is a very important crop in Costa Rica. A total

of 63,171 hectares in Costa Rica were dedicated to rice in 2009, second in area

only to coffee (Servicio Fitosanitario del Estado, Ministerio de Agricultura y

Ganadería. Sistema de Certificación Voluntario en Buenas Prácticas Agrícolas

para Productos Frescos de Consumo Nacional).

The Osa region is among the most important for rice farming in Costa Rica. We

observed rice farms within the Rio Térraba and Rio Sierpe watersheds on a scale

of artisanal farms of a few hectares to large industrial farms of thousands of

hectares. Small artisanal farms are often located within the HNTS wetland or

mangrove forest, not accessible by road, and all operations are performed by

hand. Some of the artisanal rice farmers in the Térraba region are organized into

the Asociación de Arroceros Artesanales de Térraba (headed by Dagoberto

Oconitrillo). In large farms machines are used for most operations and pesticides

are applied by plane, tractor, and with backpack sprayers. The Agrosur Company

owns the two largest farms within the Rio Sierpe and Rio Térraba watersheds

(Marcelo Aurgios, personal communication).

The Rainforest Alliance provided contact information for Sr. Oconitrillo with

whom we discussed farming practices. Most rice farms that we visited sow two

crops each year. Sr. Oconitrillo said that he plants his first crop in April and

harvests in August. He then waits 15-20 days and plants his second crop in

September and harvest in December or January. He’s been farming for 30 years.

The low price for rice in Costa Rica, driven down by cheap imports (Hermann

Fabrega, rice farmer near Rio Térraba, personal communication), is forcing some

farmers to switch to other crops. Hermann Fabrega, another farmer that we

connected with through the Rainforest Alliance, has been operating a relatively

large rice farm near the mouth of the Rio Térraba. In 2011 Sr. Fabrega planted

only one crop of rice forgoing the second crop because he had not sold his first

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crop. The low price of rice made it hard to justify to upfront expense of a second

crop. He indicated to us that soon he will be converting his rice paddy to African

Palm.

b. Pesticides use in Costa Rica with an emphasis on rice.

The list of approved pesticides in Costa Rica is constantly changing as new

chemicals enter the market and old chemicals are removed because they are

obsolete or are banned because of undue risks to humans or the environment.

Costa Rica is a signatory to the Stockholm Convention on Persistent Organic

Pollutants and ratified the treaty on 6 Feb 2007 banning many of the most

hazardous pesticides. There has been a general shift in developed and some

developing countries from long-lasting organochlorines (e.g., DDT, dieldrin) to

chemicals which may be more toxic to target organisms, but break down quickly

and have a lower potential for bioaccumulation (Carvalho 2006, Schreinemachers

and Tipraqsa 2012). The “circle of poision” is the process by which the most

dangerous pesticides are prohibited in the countries where they are manufactured

but remain legal in developing countries that export crops on which those

dangerous pesticides are used back to the countries where the pesticides are

manufactured. The list of countries in which this occurs no longer includes Costa

Rica (Galt 2008b). However, some residents of the Osa Province expressed

concern with compliance with the bans and restrictions. We heard stories that, if

true, would constitute violations of existing standards such as off label use of

chemicals or re-labeling of containers at the border.

Costa Rica does not manufacture pesticides on a large-scale, therefore most of the

active ingredients in pesticides are imported from elsewhere. The Instituto

Regional de Estudios en Sustancias Tóxicas (IRET) of the Universidad Nacional

(UNA) in Herida, Costa Rica maintains a database of pesticide imports (Muñoz

2011), which was used to develop a list of current use pesticides in Costa Rica

(Appendix Table 1). To determine which pesticides have been or are currently

used on rice we consulted peer-reviewed publications, grey literature, industry

advice, information collected during interviews with rice farmers conducted by

the Rainforest Alliance, and by reading labels on containers disposed of within

rice farms in the Rio Sierpe and Rio Grande de Térraba watersheds (Appendix

Table 2). Lab analyses also identified a few additional chemicals which may have

been used on rice or one of the other crops grown in the region.

We were not able to determine the amount of pesticide used on rice, but factors

besides crop value may necessitate the use of larger amounts of pesticide on rice

such as the regulatory risk and pest susceptibility, as well as other crop specific

circumstances (Galt 2008a).

c. Fish kills

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Figure 2. A dead robalo (Centropomus sp.)

in Estero Tajual (photo by Dagoberto

Oconitrillo on 7 Aug 2011). The fish shows

the erect fins, open gape and bulging eyes

typical of a fish killed by poisoning. Sr.

Oconitrillo said that he observed a number

of dead fish at this site shortly after

pesticides were applied to a nearby rice

farm by airplane.

Fish kills due to pesticides are nothing new to Latin America (e.g., Keiser Jr. et al.

1973, Polidoro 2007) but some of the current use pesticides are extremely toxic to

fish and shellfish (Schulz 2004). A few residents living near the Rio Sierpe and

Rio Térraba indicated that there have been fish kills in association with the aerial

application of pesticides to the larger rice farms. Sr. Oconitrillo said that there

was a fish kill one month prior to our August 2011 visit in Estero Tajual (local

name), a northern tributary of the Rio Térraba, following application of pesticides

to a rice farm just upstream from the site of the dieoff. He does not know the

name of the chemicals applied. He shared photos with us which he took at the

time of the dieoff. The photo in Figure 2 depicts a robalo with flared fins and

gills, gaping mouth and bulging eyes consistent with fish that died due to

chemical poisoning (Meyer and Barclay 1990). Geovanni Jimenez, a boat guide

out of Sierpe, also said that there are fish kills twice each year on the Rio Sierpe.

He took us to a tributary of the Estero Azul where he saw dead fish in April of

2011. He said that pesticides are applied when the rice is 15 cm (6 inches). He

does not know the name of the chemical that is applied.

One resident, who’s name was not

recorded, implicated pesticide

residues entering surface waters for

repeated die offs at the shrimp farm

within the HNTS mangrove forest.

The resident was a young employee

of one of the palm farms. The

repeated die offs ultimately lead to

the shrimp farm closing in 2011. The

assumption was that these pesticides

were from rice farms. Pesticide

poisoning has also been implicated in

die offs and reduced production at

other shrimp farms in Latin America

(Nomen et al. 2012).

Marcello Aurigos lives on Isla

Zacate at Boca Zacate, at the mouth

of HNTS. This island is about 5-8

km downstream from the nearest

farm. Sr. Aurigos makes a living by

extracting natural resources such as fish and piangua from the Humedal Nacional

de Térraba-Sierpe and the ocean. Sr. Aurgios stated that the freshwater that passes

by his island comes from both the Rio Sierpe and Rio Térraba. He knows because

he sees hyacinth which is only in the Rio Sierpe and palm and banana leaves

known from the Rio Térraba, although most of the water is from the Rio Sierpe.

He recalled with uncanny certainty that it was twenty-seven years before our

August 2011 visit when he last saw dead fish, clams, caiman and crocodiles by his

island. The die-offs occurred regularly when bananas in Sierpe were sprayed by

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plane. At that time, much of what is now planted in rice or palm was planted in

bananas. He has not noticed impacts near his island from pesticides applied to the

large rice farms upstream in the Rio Sierpe or Rio Térraba.

2. Identify and sample food fish and shellfish species

a. Identify fish and shellfish species in the Rio Sierpe likely to be consumed

We generated a list of common food fish and shellfish species based on reviews

of the literature and talks with local fishing guides. The most important marine or

diadromous fish species in the HNTS are members of the genera Caranx,

Centropomus, Diapterus, Lutjanus, and Mugil. The large characid Brycon

beherae may be taken in fresh water. The cockle Anadara tuberculosa (locally

known as piangua), a delicacy often used in ceviche, may be the most important

economic resource within the HNTS (Mainardi 1996, Sierra et al. 2007). Other

mollusks and a number of marine and freshwater shrimp species are also

harvested near the HNTS (Mainardi 1996).

We supplemented this list through discussions and observations. We quickly

came to realize that almost any species may be retained for personal consumption,

although some residents indicated that they would not retain puffers, parrot fish,

or needle fish.

Recent estimates suggest that per capita fish consumption in Costa Rica might be

very close to 6 kg per person per year, which coincides with INCOPESCA’s

marketing department’s unpublished data (FAO 2010). Although fish appear to be

an important part of the diet for most people in the Osa region, no numbers on

catch or consumption could be found to rank species importance. There is one fish

market in Palmar Norte, although in towns of this size it is typical to buy fish

from a vendor selling from a truck who shows up periodically. Both the market

and the mobile vendors sell fish brought from all over Costa Rica, including the

HNTS. Restaurants also sell fish from all over including the HNTS.

i. Tilapia

According to Bussing (2002), tilapia of the genus Oreochromis and

Tilapia, which are native to Africa, were introduced into Costa Rica for

the aquaculture industry. One guide from the town of Sierpe said that

tilapia were farmed in a pond near the Estero Azul and probably escaped

from there during a hurricane in the late 1980’s or early 1990’s (he

couldn’t remember the exact date, but possibly Hurricane Joan in 1988).

The farm is no longer in operation, but he reported that tilapia are now

found in most of the tributaries of the Sierpe. His father fishes for them by

spear as they do not bite a hook. Steve, a fishing guide from the town of

Sierpe, suggested that tilapia have been present for only a few years and

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that they may be eating freshwater shrimp. He suggested that predation by

tilapia has reduced freshwater shrimp abundance in many tributaries.

ii. Freshwater shrimp

Freshwater shrimp (Palaemonetes sp.) are eaten by locals and are used as

fish bait in the freshwater portion of the Rio Sierpe. We tried to collect

them in the Estero Azul (site 13) without luck. We had limited success in

the Estero Olla downstream of a large rice farm (site 22). Shrimp were

collected at a faster rate in the Rio Chacuaco (site 19) suggesting their

density was higher in this relatively healthy southern tributary to the Rio

Sierpe. Shrimp were also relatively abundant at the town of Sierpe

drinking water supply (site 12). During our 2009 survey, residents

indicated that shrimp are also present in the Rio Salama Viejo above the

drinking water intake for a local Finca. The residents said that poachers

used chemicals to collect them.

iii. Piangua

Piangua (mud cockel, Anadara tuberculosa) are commonly eaten in

ceviche and are a major economic resource of the HNTS. Piangua are

found on a number of mangrove islands in the HNTS that are inundated

with half to full strength sea water (Campos-Montero et al. 1990). Piangua

can be collected by hand during low tide and piangua harvest is regulated

with a minimum size of 46-47mm total length (Sierra et al. 2007). The

status of the Piangua in the HNTS has not been evaluated recently, but

thirty years ago it was relatively healthy (Campos-Montero et al. 1990).

Sr. Aurgios said that Isla Boca Brava to the north of the HNTS is no

longer good for piangua. The soil is not good and too much freshwater

passes over them. Many years ago it was better. Sr. Aurgios indicated that

there are also piangua to the south of the HNTS. Boca Llorona is part of

Corcovado Park and it is illegal to collect there without a scientific permit.

The piangua population there is healthy. It is legal to collect in Boca

Ganado and according to Sr. Aurgios the abundance is depleted due to

overharvest. There are small-scale artisanal rice farms and pastures near

the piangua islands where most farming activities are done by hand.

b. Identify locations where food fish are captured

Commercial, recreational, and subsistence fishing occurs within the estuarine

portion of the Rio Sierpe and the ocean. Recreational and subsistence fishing

occurs within the freshwater portion. During the rainy season (May-Dec.) the

local fishing guides prefer to fish for robalo (snook, Centropomus sp.) in

freshwater.

c. Conduct two sampling trips to the region Aug. 16-21 and Nov. 3-8, 2011.

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The August trip coincided with harvest of the first rice crop of the season (2

crops/year). The November trip occurred during the middle of the second growing

season. During both trips fish were sampled in a number of sites (Figure 3,

Appendix Figure 1), many of which overlap with locations where fish are caught

for consumption. By comparing pesticide residue concentrations in fish from

different locations we could determine the threat posed by fish from different

parts of the region. In one farm we sampled along a continuum starting in a ditch

within a rice farm through to the main channel.

Sampling targeted the principle fish species, although a few non-target species

were retained for analysis (Table 1). Our target list included fish of the genera

Caranx, Centropomus, Diapterus, Lutjanus, Mugil, and Oreochromis, the cockle

Anadara tuberculosa, and the freshwater shrimp Palaemonetes sp. In August

2011, we also sampled some characids and poecilids that were present in the

canals in rice farms even though they were not indicated to be food fish.

Sites were accessed by boat or vehicle as appropriate. We procured the assistance

of local fishing guides and residents throughout the HNTS to identify and access

sampling sites. Sr. Oconitrillo and Sr. Auguros took us to sample piangua

(cockles, Anadara tuberculosa) in the Humedal Nacional Térraba-Sierpe during

the August 2011 sampling trip. Fish were sampled by hook and line, 0.6 cm mesh

cast net, 0.6 cm mesh beach seine, 7.6 cm mesh gill net and by purchasing fish

directly from fisherman or from a fish market (See Appendix Figure 1 for the gear

used at a particular site). We also harvested piangua by hand at three locations in

the HNTS. Total lenth and weight was recorded on the day of capture. Species

identification was primarily done by WHE from fresh or preserved specimens or

photographs with the aid or regional ichthyofuanal guides and past experience.

Dr. Ross Robertson at the Smithsonian Tropical Research Institute was consulted

to resolve the specific identity of Lutjanus.

A total of 301 individual fish and shellfish were collected during the two trips

(Table 1). Noteworthy collections include several species of robalo (snook,

Centropomus sp.) in fresh, brackish, and ocean waters and the marine species

pargo colorado (red snapper, Lutjanus colorado) at two freshwater sites in the Rio

Sierpe. We also collected quite a few tilapia (Oreochromis niloticus), a freshwater

species, in canals draining a large rice farm on the Rio Sierpe. Additional species

and their sampling locations are indicated in Table 1.

Tissue samples for pesticide analysis were taken from large fish the same day

they were captured by removing the filet from both sides of the fish or a portion

of the filet near the head. Smaller fish were processed whole. All utensils and

surfaces were washed with diethylether and allowed to dry before removing the

tissue sample and processing took place on a fresh piece of muffle furnace

cleaned aluminum foil to avoid cross contamination. Fish tissue samples were

individually wrapped in cleaned aluminum foil. Unshucked piangua and whole

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shrimp from a single sampling event were combined and wrapped in cleaned

aluminum foil. All samples were stored frozen until reaching the SWRC

laboratory in the US. At the SWRC laboratory, skin-on filets were removed from

remaining fish, and piangua were removed from their shell. Shrimp were left

whole. Diethylether was used to clean all utensils between samples and

processing took place on a fresh piece of clean aluminum foil for each sample to

avoid cross contamination. A 10-20g sample of individual or composited skin-on

filet, whole clam or whole shrimp was placed in a borosilicate vial and stored

frozen (-20°C).

3. Evaluate variation in pesticide residue concentrations within and among species

and sites

a. Measure pesticide residue levels in fish and shellfish

This report presents the results of pesticide analyses of 45 individual or

composited fish or shellfish samples collected from 19 locations in the Rio Sierpe

and Rio Grande de Térraba, the Térraba-Sierpe Mangrove Forest, and from the

ocean in August or November 2011 (Table 2). (No fish of shellfish from sites 5, 8,

9, 11 or 16 were tested). A total of 41 individual descaled skin-on fish filets or

composited piangua samples were analyzed for 63 organochlorine,

organophosphate, triazine and pyrethroid pesticides or their derivatives using a

standard protocol (EPA-821-R-08-001, Method 1699: Pesticides in Water, Soil,

Sediment, Biosolids, and Tissue by HRGC/HRMS) by AXYS Analytical

Services, Ltd. in Sydney, British Columbia (method MLA-035; Table 3). Two

additional composited piangua samples and two composited shrimp samples were

analyzed for 29 organochlorine chemicals using high resolution gas

chromotagraphy with mass spectroscopy (AXYS Analytical Services, Method

MLA-028; Table 3). Frozen tissue samples were shipped overnight on wet ice

from the SWRC to AXYS Analytical Services. All samples were still frozen upon

arrival. All tissue processing, spectroscopy and data quality control was

conducted at AXYS Analytical Services. Lipid concentration was also determined

as part of the pesticide analysis.

b. Legacy pesticides persist throughout the study area

A total of 34 of 63 chemicals were detected in fish or shellfish representing the

active ingredient or breakdown product of 20 different pesticides (Table 4,

Appendix Table 3). Eight of the 20 pesticides detected are legacy pesticides that

have been banned in Costa Rica for decades. Three restricted use pesticides were

also detected.

The pesticides that were detected in the most locations were the banned pesticides

Dieldrin and Hexachlorobenzene, along with the restriced use pesticide

Endosulfan, which were each found in fish or shellfish from 18 of 19 sites and the

fish market (Figure 5). The banned pesticides Chlordane, DDT, Endrin,

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Heptachlor and Mirex were also common being detected in 9 or more sites.

Banned and restricted use pesticides persist throughout the study area.

Most current use pesticides were found in fewer sites. Chlorphyriphos was found

in 10 sites, Chlorothalonil in 7 sites and Diazinon in 4 sites. The current use

pesticides Ametryn, Atrazine, Captan, Cypermethrin, Octachlorostyrene,

Permethrin, Primiphos-methyl, Quintozene and Terbufos and the banned pesticide

beta-HCH (a breakdown product of Lindane) were all rare each being detected in

only 1 or 2 sites.

c. Species differences in pesticide residues

All samples contained detectable levels of at least 1 and as many as 25 chemicals

(Appendix Table 3). The concentration of organochlorines was highest on average

in tilapia, followed by bagre (sea catfish) and machaca (Figure 4). The bagre

contained the highest average concentration of triazines, organophospates, and

pyrethroids, but it should be noted that only one composite bagre sample of three

small individuals was screened. The variability of pesticide concentrations within

and among species could reflect differences in a number of intrinsic factors,

including size, age, growth rate, diet, feeding rate, tissue composition, migration

patterns, and the size of the home range (Borgå et al. 2004).

i. ANCOVA

An analysis of covariance (ANCOVA) considering species, lipid content

and length revealed that species was the only consistent predictor of

pesticide concentration among the four classes of pesticides (Appendix

Table 3). Lipid content was a significant predictor of organochlorine and

pyrethroid concentration. Length was a significant predictor only with

pyrethroids in interaction with other terms.

ii. Lipids

Most of the pesticides are lipid soluble and, in general, pesticide residue

concentration increased with the lipid content of the organism (Figure 4).

Machaca, which had the highest lipid levels of the species examined, also

contained relatively high concentrations of most pesticides. Tilapia and

bagre also had high lipid levels and high concentrations of some

pesticides.

Camarones (shrimp) were an exception to this pattern. They had high lipid

levels but did not exhibit high concentrations of pesticides. Other factors

which could account for the relatively low pesticide concentrations in

camarones could be the ambient concentration in the locations where they

were sampled or their higher sensitivity to contaminants resulting in

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mortality of individuals before they attain a large body burden (Schulz

2004, Nomen et al. 2012).

iii. Size & age

Size and age are two of the more important factors that can influence the

concentration of contaminants in biota because many contaminants can

bioaccumulate over time. Bioaccumulation is the process that causes an

increased chemical concentration in an organism compared to that in its

ambient environment, through all exposure routes including dietary

absorption and transport across body surfaces (Borgå et al. 2012).

Bioaccumulation is a rate dependent process, so if the rate of chemical

absorption exceeds the rate of elimination or dilution due to growth then

the chemical concentration will increase over time. Therefore, older fish

would be expected to have a higher body burden than younger fish/

We did not age fish in the course of this study, so we considered the

relationship between size and pesticide burden. Tilapia exhibited a weak

positive relationship between size and pesticide burden but other species

did not (Figure 4). In fact, the sea catfish, which were fairly small and

probably young of the year, contained some of the highest observed

concentrations of many pesticides.

Failure to detect a strong relationship between size and pesticide burden

should not be taken as an indication that bioaccumulation is not occurring.

Rather, it suggests that the rates of pesticide absorption, elimination and

dilution are variable throughout the life of an individual fish.

iv. Diet

Biomagnification can be regarded as a special case of bioaccumulation in

which the chemical concentration in the organism exceeds that in its prey

due to dietary absorption occurring faster than elimination (Borgå et al.

2012). Biomagnification would result in a sequential increase in

contaminant concentrations with an increase in trophic level (Kidd et al.

1998). The often observed relationship between trophic level and pesticide

burden has prompted the investigation and development of trophic

biomagnification factors to predict pesticide burden based upon

knowledge of trophic level (Borgå et al. 2012).

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Species Diet

Tilapia Herbivore

Piangua Organic matter

Camarones Organic matter

Machaca Omnivore

Bagre Omnivore

Pargo Carnivore

Robalo Carnivore

Tilapia has a predominantly vegetarian diet and machaca is an omnivore

eating fruit and seeds that fall into the water as well as small fish and

invertebrates (Bussing 2002). Robalo and pargo are both carnivores that

eat fish and shrimp (Bussing 2002). Piangua and camarones are both filter

feeders that probably consume a combination of plant and animal matter.

Based upon the trophic biomagnification model of pesticide

bioaccumulation, tilapia would be expected to have the lowest

concentration of most pesticides among the fish species, followed by

camarones and piangua and then machaca. Robalo and pargo would be

expected to have the highest concentrations of pesticide residues. The

species are ordered in the table above by their expected relative

concentration of pesticides from lowest to highest, based upon trophic

magnification.

Pesticide residues were not higher in fish that occupy the highest trophic

level (Figure 4) indicating that trophic biomagnification was not a primary

driver of pesticide accumulation among the fish in this study. The results

suggest that tilapia and bagre consume more contaminated material than

most other species, including robalo and pargo.

v. Size of home range

The potential for the concentrations of pesticide residues to increase or

decrease in the tissue of exposed organisms depends in part upon the

ambient concentration. The rate of absorption from the diet or diffusion

across the body surface may exceed the rate of elimination or dilution

when fish are in an area with a high ambient concentration, in which case

the pesticide concentration increases. Outside of these hot spots

elimination or dilution due to growth may exceed absorption, in which

case the body burden declines.

The size of an organism’s home range may influence its pesticide body

burden if the ambient concentration of a pesticide is spatially variable.

Organisms with a restricted home range would reflect the average ambient

concentration in a single location, which may be high or low. Organisms

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that are more wide ranging may move between areas with high and low

ambient concentration and therefore reflect the average concentration

across a broader geographic area.

Species Home range

Piangua Estuary sedentary

Camarone Freshwater resident

Machaca Freshwater migrant

Bagre Estuary resident

Pargo Diadromous

Robalo Diadromous

Tilapia Freshwater resident

The home range of fish in Costa Rica has not be studied extensively, but

based upon the species life history and evidence from elsewhere, robalo

would be expected to have the largest home range of the fish species

examined and tilapia the smallest. Robalo are diadromous capable of

tolerating both fresh and salt water. In Florida, most adults migrate

between fresh and salt water annually for spawning (Trotter et al. 2012).

Pargo also appear to be diadromous – they were captured in both fresh and

salt water – but probably spend less time in freshwater than robalo. Tilapia

is a resident species and individuals probably exhibit a restricted home

range. The home range of machaca is not known, but this freshwater

species migrates into small streams to spawn and apparently can tolerate

some salt water, therefore its home range may be somewhere between

tilapia and robalo. Elsewhere in the tropics, camarones migrate to

headwater streams (Greathouse et al. 2006), which may also occur here

suggesting that their home range may include more than one stream or

stream segments.

Resident tilapia had either a high or low pesticide concentration, as

expected. For example, at site 10 where a number of highly contaminated

fish were collected, tilapia, which probably exhibit limited movement

within a segment of river, usually contained the largest number and the

highest concentrations of pesticides. The highly mobile Robalo from site

10 contained fewer pesticides at lower concentrations. Machaca from site

10 were intermediate in concentration suggesting that they may display

movement somewhere between tilapia and robalo. The same pattern was

observed in Estero Azul where the machaca had higher concentrations of

most pesticides than did the robalo. These results are consistent with the

hypothesis that migratory fish moved between areas with high and low

ambient pesticide concentrations, whereas resident fish remained fixed.

When the ambient concentration of pesticide residues is highly variable

home range size and location may be more important than other intrinsic

factors such as size or trophic level.

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In summary, lipid content and the relative size of the species home range are two

important intrinsic factors that appeared to influence the concentration of

pesticides residues in fish and shellfish in the Osa Province. Diet and the length

of the individual were not as important. The relationship between pesticide

concentration and lipid content is not surprising considering that many of the

pesticides are lipid soluble. The connection with the size of the home range

suggests that the ambient concentration of pesticides is highly variable in the

study area. Spatial variability in pesticide absorption and elimination could

explain why highly mobile species with large home ranges, such as robalo, had

lower contaminant levels than tilapia, which generally have a more restricted

home range, even when they were sampled in the same location. Although diet

did not appear to be important, there may also be important ontogenetic shifts in

life history behavior which affect pesticide accumulation. For example, species

like robalo may eat fewer contaminated food items when they shift from a

freshwater to marine phase.

d. There are hot spots for most pesticides

At least one pesticide was detected in fish and shellfish from all sites, but the

concentrations were quite variable among sites (Figure 5). Differences in the

concentrations of pesticides among fish from different sites likely reflect

differences in the ambient concentration of the pesticides. The highest observed

concentration of any chemical was of DDT in one Tilapia from site 10 (Puerto

Cortez) which reached 49 ng/g wet weight. Cypermethrin, Dieldrin and

Endosulfan each were observed above 7 ng / g wet weight in at least one sample,

and Atrazine, Chlorpyrifos, Diazinon and Permethrin reached a maximum

concentration of 2.1 - 5.7 ng/g wet weight in at least one sample. Twelve other

pesticides did not exceed 1.1 ng/g wet weight in any sample.

Two locations stood out as hot spots for fish contaminated with banned pesticides,

a tributary to the Rio Térraba near Puerto Cortez (site 10) and the Estero Azul in

the Rio Sierpe (sites 13 and 14). Both locations contained fish with relatively high

concentrations of Chlordane, DDT, Dieldrin, Endrin and Heptachlor. Other

chemicals found only in the Estero Azul were Octachlorostyrene, Primiphos-

methyl and Terbufos. beta-HCH (a breakdown product of Lindane) was detected

only in a fish from Puerto Cortez. Both tributaries drain urban and agricultural

areas, including rice farms, and are inundated with water from the respective

mainstem rivers during high tide. This matches a world wide pattern where

organochlorine contaminated soils are often near urban areas (Bezama et al.

2008).

The lower Rio Terraba including the nearby mangrove island at Boca Brava (sites

2, 6 and 10) was a hot spot for Chlorpyrifos and Endosulfan, where

concentrations exceeded what was observed in the Rio Sierpe.

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A number of current use chemicals – Atrazine, Ametryn, Captan, Cypermethrin

and Quintozene – were most abundant near active rice farms (Sites 6 and 10 in the

Rio Terraba and sites 14 and 15 in the Rio Sierpe). Diazinon, another current use

pesticide, was also found at most of these sites as well as a few nearby sites (site 2

near the Rio Terraba and site 19 in the Rio Sierpe) suggesting that it had spread

since application.

Mirex and Hexachlorobenzene, two banned pesticides, were the only two

pesticides found in samples from most locations and the fish market, at

equivalent, albeit low, concentrations (<0.2 ng/g wet weight).

e. Fish in rice farm canals contain lower than average concentrations of banned

pesticides.

To evaluate the threat that farming practices pose to consumers we sampled

tilapia in three ditches with active stream flow draining a large rice farm on the

Rio Sierpe (sites 15, 20 & 21). We also sampled robalo and machaca further

downstream in the Estero Azul (sites 13 & 14).

The fish with the highest concentrations of banned pesticides were not in streams

immediately adjacent to rice farms. Tilapia from the three sites within the rice

farm all had lower concentrations of banned pesticides than were observed in

other fish species sampled further downstream. For instance, the tilapia had lower

concentations of Chlordane, Chlorothalonil, DDT, Dieldrin, Endrin, Heptachlor

and Mirex than the machaca and a robalo sampled downstream in the Estero Azul.

On the other hand, a tilapia from site 15 contained a much higher concentration of

Diazinon, a current use pesticide. Diazinon is water soluble and highly toxic to

fish and it is possible that the fish community present when we sampled the

ditches consisted of individuals that recolonized since the most recent pesticide

application, and therefore were still accumulating contaminants.

Finding lower concentrations of banned pesticides in fish within the rice farms

than outside of the farms suggests this farm has been following the bans and that

the source for persistant organic pollutants is somewhere else in the watershed,

possibly in the downstream sediment.

f. Concentrations of legacy pesticides are declining

Many of the chemicals that were detected in this study are currently banned in

Costa Rica. However, the observed tissue concentrations of these chemicals do

not suggest that there has been recent application in violation of existing bans;

rather the observed concentrations are consistent with contamination from

persistent legacy residues.

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To demonstrate how far concentrations of banned pesticides have declined, we

evaluated long-term trends in contaminant concentrations by comparing the

concentrations we observed in 2011 with what has been observed previously. No

data could be found for biota from the Osa Region, therefore we relied on

observations from other parts of Latin America that had a similar history of

intensive agriculture.

The average and maximum concentration of DDT in many of the same species

sampled along the Pacific Coast of Guatemala in 1970 was 4,200 and 45,000 ng/g

wet weight (Keiser Jr. et al. 1973), about 1,000 times higher than the average and

maximum concentrations we observed.

More recently, the concentrations of DDT observed in other regions of South

America with a similar history of intensive agriculture were similar to the

concentrations we observed (Barra et al. 2006).

Long-term monitoring in El Salvador revealed that not all pesticides are declining

in concentration as expected (Nomen et al. 2012). While the concentration of

DDT at fixed monitoring stations has declined since the 1970’s, the concentration

of Dieldrin has not changed suggesting that a different source of contamination

may be impacting the sampling site. It is interesting that both that study, as well

as our own, found Dieldrin to persist in the environment.

g. There may be seasonal changes in pesticide concentrations in biota – heavy rains

may dilute pesticides but increase transport distance

We conducted a reciprocal transplant experiment with piangua to evaluate sources

and rates of accumulation of pesticides in the HNTS mangrove forest. Piangua

from a presumed “clean” site near the Boca Zacate (site 4), which is dominated by

flow from the Rio Sierpe, were collected in August and placed in mesh bags and

swapped with piangua from Isla Boca Brava (site 2), which is dominated by flow

from the Rio Térraba and which we thought would be a “dirty” site. Three bags

with 10 piangua each were transported to the Boca Brava and two bags with 5-6

piangua each were transported to Boca Zacate. We also attempted to exchange

piangua with an island near Boca Chica (site 3), but lost the transplanted piangua

to predation. The piangua were retrieved 11 weeks later in November.

In August, piangua at each site contained detectable concentrations of four

pesticides and a total of six pesticides were detected across all sites (Table 4).

Among the pesticides detected at more than one site, concentrations of

Endosulfan and Hexachlorobenze were higher at the sites closer to the Rio

Térraba supporting out hypothesis that this river was more “dirty”.

Pesticide concentrations generally declined in both locations during the transplant

experiment. Fewer pesticides were detected in the November samples compared

to the August samples and the pesticides that were detected were often at lower

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concentrations (Table 4). These results suggest that the pesticides were being lost

from the animals by dilution. There were two exceptions, however. Piangua from

Isla Zacate that were transfered to Isla Boca Brava accumulated Endosulfan and

Mirex, although Mirex was not detected at any of the sites in August. Likewise,

piangua from Isla Boca Brava accumulated Dieldrin at Isla Zacate even though

Dieldrin was not detected at Isla Zacate in August.

The mangrove islands where piangua are found may be 5 km or more from the

nearest industrial farm, although artisanal farms may be closer to the islands. In

general, piangua contained fewer chemicals at lower concentrations than fish and

shellfish samples that were collected closer to an industrial farm. However, the

increase in concentration of some pesticides in the piangua between August and

November suggests that the threat of pesticides extends beyond the immediate

farm where it was applied.

The rainy season is likely to have a complex spatial and temporal affect on

pesticide concentrations. Heavy rains may increase runoff leading to a temporary

spike in ambient pesticide concentration near the source (Anasco et al. 2010).

However, increased volume of surface waters may decrease the concentrations of

some pesticides in biota by diluting the ambient concentration (Nomen et al.

2012) causing the rate of elimination to exceed the rate of absorption. But our

study suggests that heavy rains may also increase the transport distance of

pesticides thereby increasing the concentration in biota at sites that are far from

the source, which could have contributed to the increase in concentration of

Dieldrin, Endosulfan and Mirex we observed.

h. Atmospheric transport of pesticides

To evaluate the threat posed by pesticides being transported through the air to a

remote site and accumulating in biota there, we tested freshwater shrimp from the

town of Sierpe drinking water supply (site 12). We detected three legacy

pesticides in the freshwater shrimp: DDT, Hexachlorobenzene and Mirex (Table

4). The drinking water supply is relatively undisturbed and there is no agriculture

upstream of the drinking water supply, so the most likely mechanism for

pesticides to enter the biota in this stream is via aerial transport and deposition.

Transport and deposition of pesticides is generally associated with aerial

application from a nearby farm (particularly during a rain storm, (Standley and

Sweeney 1995, Daly and Wania 2005, Daly et al. 2007a, 2007b), but these

chemicals are banned in Costa Rica so they may not have been applied for

decades. Residual chemicals remaining in the soil of the farms may get swept up

and transported by a passing storm. Alternatively, the chemicals may be in the

soil adjacent to the drinking water supply or in the stream sediment. In any event,

observing banned pesticides in the Sierpe drinking water supply suggests an

alternate route of exposure, and that the threat of pesticides persists long after

their use has stopped.

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i. Chlorothalonil

Chlorothalonil displayed an unsual distribution (Figure 5). This current use

fungicide was found in 5 of 6 Machaca from the freshwater or estuarine study

sites (not found in site 19, the Rio Chacuaco), but not in any other species from

the freshwater or estuarine locations. It was also found in a pargo from the ocean

and a robalo from the fish market in Palmar Norte. It is possible that the

omnivorous diet of Machaca would make them more susceptible to ingesting this

pesticide than the other species in the HNTS (they are omnivorous and feed on

seeds and fruits that fall into the water). Alternatively, this chemical binds to lipid

and, because machaca tended to have the highest percent lipid composition, this

could account for the presence of this pesticide in Machaca.

4. Evaluate risk to consumers from eating contaminated food fish and shellfish.

We evaluated the threat to consumers from eating contaminated fish or shellfish

using standards developed by the U.S. Environmental Protection Agency. The

USEPA has broken down health effects posed by contaminants into non-

carcinogenic and carcinogenic effects (USEPA 2000). The concentration of a

contaminant which results in a carcinogenic health effect is not always the same

as the concentration which results in a non-carcinogenic effect. In addition, in the

U.S. the acceptable risk of carcinogenic and non-carcinogenic effects (that is the

proportion of the population which may experience a health effect) may be lower

or higher than elsewhere. Therefore the protocol and consumption advisories

presented here may need to be adjusted to meet standards in Costa Rica.

“Noncarcinogenic effects resulting from multiple exposures occurring over a

significant period of time are also termed chronic exposure effects (IRIS 1999).

The RfD is defined as “an estimate (with uncertainty perhaps spanning an order of

magnitude) of daily exposure to the human population (including sensitive

groups) that is likely to be without an appreciable risk of deleterious effects

during a lifetime (USEPA 1987; USEPA 2000 V2 p2-14). The use of the IRIS

RfDs is recommended for evaluation of chronic exposure toxicity of the target

analytes. RfDs calculated for chronic noncarcinogenic effects reflect the

assumption that, for noncarcinogens and nonmutagens, a threshold exists below

which exposure does not cause adverse health effects.” (USEPA 2000)

USEPA (2000) Equation (3-3) was used to calculate the allowable daily

consumption (CRlim) of contaminated fish, based on a contaminant’s

noncarcinogenic health effects, and is expressed in kilograms of fish per day:

Eq. 1

CRlim = Maximum allowable fish consumption rate (kg/d)

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RfDm = Reference dose of chemical contaminant m (mg/kg-d)

BW = Consumer body weight (kg)

Cm = Observed concentration of chemical contaminant m in a given species of fish

(mg/kg)

Fish may contain multiple contaminants simultaneously and health advisories

should account for possible toxic interactions. Very little data are available on

toxic interactions, so determining the type of interaction remains partially a matter

of guesswork. Contaminants in a mixture that induce the same health effect by

similar modes of action (e.g., cholinesterase inhibition), may be assumed to

contribute additively to risk (USEPA 2000). Chemicals in a particular class (e.g.,

organochlorines or organophosphates) tend to have a similar mechanism of

toxicity and produce similar effects. For mixtures of chemicals that produce

similar toxicological endpoints, USEPA recommends dose addition (USEPA

2000 V2 p 3-20). When information is lacking on joint effects in the same organ,

a conservative approach is to assume dose addition (USEPA 1999 –EPA/630/R-

00/002 August 2000, Supplementary Guidance for Conducting Health Risk

Assessment of Chemical Mixtures). For calculating consumption limits based on

non-carcinogenic effects, we assumed dose addition for effects of all components

in chemical mixtures. The equation for dose additivity of noncarcinogenic effects

is:

Eq.2

If different fish with different concentrations of a mixture of chemicals will be

eaten then the equation for determining the daily consumption limit will be:

Eq.3

where Cm,j is the concentration of chemical m in fish j, Pj is the proportion of

species j in the meal and .

Some of the chemicals also pose a cancer risk, therefore we calculated the

allowable daily consumption (CRlim) of contaminanted fish based upon a

contaminant’s carcinogenic health effects, expressed in kilograms of fish per day

using USEPA (2000) – Equation (3-1):

Eq.4

CRlim = Maximum allowable fish consumption rate (kg/d)

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ARL= Maximum acceptable individual lifetime risk level (unitless)

BW = Consumer body weight (kg)

CSFm = Cancer slope factor, usually the upper 95 percent confidence limit on the linear

term in the multistage model used by EPA ([mg/kg-d]-1

).

Cm = Observed concentration of chemical contaminant m in a given species of fish

(mg/kg)

For calculating consumption limits based on carncinogenic effects of multiple

chemicals, we assumed dose addition for effects of all components in chemical

mixtures. The equation for dose additivity of carcinogenic effects is:

Eq.5

If different fish with different concentrations of a mixture of chemicals will be

eaten then the correct equation for determining the daily consumption limit will

be:

Eq.6

It is often easier to comprehend risk when expressed as a monthly consumption

limit. We used USEPA (2000) Equation (3-2) to calculate the monthly

consumption limit:

Eq.7

where Tap is the number of days in an average month or 30.44 days and MS is the

average meal size.

The RfD and Cancer slope factor for each chemical was retrieved from the EPA

Integrated Risk Information Service (www.epa.gov/IRIS) in September 2012

(Table 5). We used the USEPA (2000) recommended ARL of 10-5

, an average

meal size of 227 g (0.5 lb) and assumed a body weight of 70 kg (154 lbs). We

calculated consumption advisories only for contaminants and their breakdown

products that had detectable concentrations.

a. The risk to consumers is highest near Puerto Cortez (Rio Térraba) and the Estero

Azul (Rio Sierpe)

Averaging pesticide concentrations in individuals of the same speices from the

same site and month resulted in a total of 32 sites/season samples. Food fish in a

tributary to the Rio Grande de Térraba near the town of Puerto Cortez and in the

Estero Azul on the Rio Sierpe are contaminated with pesticide residues that could

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threaten consumers (Table 6). In the U.S.A., the observed concentrations would

lead to restricted consumption advisories for machaca (machaca or sabalo, Brycon

behreae, 0.7-1.1 meals per month), tilapia (tilapia, Oreochromis niloticus, 3.6

meals per month) and robalo aleta manchada (blackfin snook, Centropomus

medius, 6.5 meals per month) for fish caught in these two locations. Other species

such as pargo calorado (red snapper, Lutjanus colorado), bagres (sea catfish,

Cathorops sp.), camarones de aqua dulce (freshwater shrimp, Palaemonetes sp.),

and piangua (cockles, Anadara tuberculosa) from elsewhere in the Humedal

Nacional Térraba-Sierpe, the freshwater portion of the Rio Sierpe or Rio Térraba,

or from the ocean near the Rio Sierpe are safe to eat in unlimited quantities (i.e.,

>16 meals per month).

We made a number of assumptions about a consumer’s exposure to chemical

contaminants. These recommendations are based upon 227 g (0.5 lb) of skin-on

fish filet, whole clam or whole shrimp per meal and apply to a 70 kg (154 lbs)

person. We assumed that consumers were eating raw skin-on filets that had been

descaled. Removing the skin and fatty portions of the fish may result in lower

concentrations of lipid soluble chemicals (USEPA 2000). Also cooking filets may

result in a reduction in the concentration of lipid soluble contaminants because fat

tends to be lost during cooking (USEPA 2000). Alternatively, soups made from

whole fish including the head and organs may increase the consumer’s

contaminant exposure to organic pesticides because these tissues tend to have

higher lipid levels than do filets (USEPA 2000). Cleaning or cooking that reduces

the fat content, where most of the pesticides are stored, may reduce the risk to

consumers, whereas consuming the head or organs may increase the risk to

consumers.

We assumed that the only source of exposure was by eating contaminated fish.

Other potential sources of exposure include water, soil, air or other contaminated

foods. Agricultural workers who live and work near areas where pesticides are

applied may be exposed to higher amounts of contaminants and therefore would

want to further restrict their consumption of contaminated foods beyond the

recommendations here. Other routes of exposure such as water, soil, other foods,

or occupational exposure may increase the risk to consumers (Polidoro et al.

2008).

b. Diledrin is the most significant driver of the consumption advisories.

The concentration of Dieldrin on its own would be sufficient to warrant the

consumption advisories in all four cases where they are warranted. The only other

pesticide that would warrant a consumption advisory on its own was DDT in

Tilapia near Puerto Cortez (site 10), although the risk posed by Dieldrin is still

higher for this fish. No other chemical was at a sufficient concentration to warrant

a consumption advisory on its own.

5. Develop an understanding of water physiochemistry

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We were able to take advantage of having visited multiple sites in the Rio Sierpe,

lower Rio Grande de Térraba and Humedal Nacional Térraba-Sierpe to describe

water physiochemistry throughout the region. Stream physiochemistry can influence

community structure of aquatic organisms and influence spawning or feeding

behavior, growth and population dynamics, as well as the transport of contaminants.

a. The Térraba and Sierpe differ in many physiochemical characteristics.

The mainstem of the Rio Térraba contains higher dissolved oxygen concentrations

(DO), turbidity, and pH, but lower specific conductivity, particularly upstream of

tidal influence (Figure 6). In comparison, the mainstem and some tributaries to the

Sierpe are depleted in dissolved oxygen. Temperature is similar in the two

mainstems upstream of tidal influence.

b. There are strong seasonal differences in water physiochemistry related to

changes in the amount of freshwater in streams in rivers.

More freshwater enters streams, rivers and the mangrove estuary during the rainy

season than during the dry season. We noted that saltwater intrusion into the

mangrove estuary during high tide does not extend as far during the rainy season

because the much larger discharge from the rivers keeps the saltwater lens from

extending upstream. However, there is greater intrusion of saltwater into the Rio

Sierpe portion of the estuary because this river has less discharge than the Rio

Térraba. During the rainy season the Térraba mainstem is extremely turbid and

influences a greater proportion of the mangrove estuary than does the Rio Sierpe.

Sr. Geovanni Jimenez stated that most of the water from the Rio Sierpe enters the

ocean through Boca Guarumal, which is to the south of Boca Zacate.

IV. CHALLENGES OR OBSTACLES

We could not test for the presence of all of the pesticides of interest (particularly current use

pesticides) due to not finding a laboratory capable of screening some chemicals. Some of the

pesticides of interest are known to be in use by a number of farms in large quantities (e.g.,

Propanil and Mancozeb). Many of these chemicals breakdown rapidly and may not

accumulate in fish or shellfish (e.g., Mancozeb: EPA 738-R-04-012). Some chemicals, such

as Propanil or its metabolites, may accumulate in fish or shellfish and may pose a health risk

to human consumers (Propanil: EPA-HQ-OPP-2003-0348). Many of these pesticides are also

highly toxic to fish, crustaceans, and molluscs.

The list of pesticides used on rice may not be complete. Chemicals may not be listed because

of non-reporting by farmers when their use is illegal or off-label. We also experienced

difficulty connecting with local ecotoxicologists working on similar questions at the

Universidad Nacional in Heridad.

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We intended to target a number of fish species for contaminants analysis but we had

difficulty catching some species in sufficient numbers. This may be because there are few

fish available to catch or because of limitations of our equipment or technique. Low

abundance could be a problem in the vicinity of rice farms where recent fish kills may have

reduced abundance. We were told that fish die offs are common and in some areas occur

twice a year in association with the aerial application of pesticides to rice farms. Abundance

may also vary naturally due to seasonal cycles in life history. Fishing is poorly regulated in

these areas and overfishing may also be reducing abundance. Future research should be

aimed at determining the status of important food fish in the HNTS.

Future research should explore pesticide transport in the region. A number of factors could

influence the amount of pesticide entering surface waters including: pesticide type, amount,

and time since last application; timing and method of pesticide application; weather and soil

type; proximity to surface water and factors that affect runoff including status of riparian

buffers, slope of the terrain, or presence of retention ponds.

The frequency of fish kills suggests that another threat posed by rice farming may be to the

food supply. Toxicity data is based upon summaries of other studies conducted elsewhere,

usually with temperate fish species from North America or Europe. Toxicity data may not be

directly applicable to tropical fish species found in Costa Rica where differences in climate

(rain, temperature), animal species (air breathing), and crops (e.g., rice, hillslope coffee,

bananas) could result in different affects to fish (Lacher and Goldstein 1997, Daam and Van

den Brink 2010). Future monitoring should evaluate the impact of pesticide application on

fish, particularly with regard to episodic fish kills.

It is also important to determine the factors that contribute to low levels of dissolved oxygen

within the Rio Sierpe. During a previous BMF funded project in the Rio Sierpe we observed

dissolved oxygen levels close to 0 mg/L within the headwaters of the Rio Sierpe at the end of

the dry season in April 2009. This concentration of DO is below the level required for most

aquatic organisms. The macroinvertebrate community at this site exemplified anoxic

conditions and consisted almost exclusively of blood red chironomids (i.e., species that are

extremely tolerant of low dissolved oxygen). During a trip in August 2011 the oxygen level

at this location was higher, and increased when a rainstorm passed (Appendix Figure 2),

although the concentration may still be below the concentration required for many aquatic

organisms. The concentration of dissolved oxygen was also well below saturation at the town

of Sierpe where the river is much larger (Appendix Figure 3). Low dissolved oxygen in such

a large river can occur if there is poor aeration due to insufficient mixing and water clarity is

low, which limits in-stream production of oxygen by photosynthesis, and warm waters are

combined with heavy loads of organic mater and nutrients, which increases the consumption

of oxygen by the microbes that feed on the organic matter.

V. FUTURE

A thorough evaluation of the threat to humans from eating contaminanted fish and shellfish

and development of guidelines to reduce those threats requires more information. Following

is a description of some of those information needs.

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1. Severe health effects or death due to acute pesticide poisoning is rare in Costa Rica

(Litchfield 2005, Wesseling et al. 2005), however chronic effects may be common and

cancer rates in the Osa Province are among the highest in Costa Rica, particularly for

women (Wesseling et al. 1999). Additional information is needed on consumer behavior

to more accurately evaluate threats of eating contaminated fish within Osa Province,

Costa Rica. Information needs include: Where are food fish for commercial (i.e., sold at

local fish markets) versus private consumption captured? What type and amount of fish

are eaten by local inhabitants? How are fish prepared? Of all the places we visited, we

observed the largest number of people fishing in the tributary near Puerto Cortez where

some of the most contaminanted fish are located. People catching fish for consumption

near Puerto Cortez and Estero Azul may need to be informed of the health risks

associated with consuming fish from these waters.

2. Efforts should be undertaken to minimize the risk posed by legacy pesticides and current

use pesticides to aquatic biota and potential consumers of contaminanted food. A

comprehensive approach will entail reducing the amount of pesticide used, such as by

implementing integrated pest management protocols, using alternatives to hazardous

pesticides, and restricting pesticides from entering surface waters. Restricing pesticide

transport to surface waters will require an understanding of runoff and aerial deposition,

and the possible role of riparian buffers, constructed wetlands or vegetated channels in

slowing pesticide transport and facilitating breakdown (Schulz 2004). Heavy rains may

reduce the impacts of pesticides by diluting the concentration in the surface waters.

However, rain may increase the transportation distance of pesticides as more pesticides

are likely to be washed off of fields, and pesticides suspended in the water column are

likely to be transported further downstream. In addition, pesticides that are applied from

a plane during a rain storm are more likely to be carried to remote locations. The

Rainforest Alliance has done an exemplary job of working with local farmers to identify

incentives to minimize the risk of pesticies and should be encouraged to continue to do

so.

3. Legacy pesticides persist throughout the region but our results suggest that the threat to

consumers from eating contaminated fish or shellfish may be declining due to a shift

towards pesticides that breakdown or leave the system quickly, or pose a low health risk

to consumers. However, threats to the regional fisheries resource may remain high due to

episodic localized fish kills during and immediately after pesticide application. Future

research should evaluate the risk of fishery collapse of highly desirable species due to

unregulated fishing and periodic fish kills (likely resulting from pesticide application)

coinciding with the breeding season. Species traits, such as toxilogical sensitivity at

different life stages, generation time and home range, may prove useful to identify

species most at risk and to evaluate community effects of surface water contamination

(Liess et al. 2008).

4. A great deal of concern arose in 2012 in the US and Sri Lanka when arsenic and other

heavy metals were detected in rice (USFDA 2012, Johnson et al. 2012). In Sri Lanka,

arsenic and other heavy metals have been linked to a rare chronic kidney ailment

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(Johnson et al. 2012). The arsenic appears to be a contaminant in the pesticides that are

applied to rice. Arsenic in pesticides may also be entering nearby surface waters and

contaminating food fish and shellfish. However, concentrations of arsenic in edible fish

in some reservoirs in Sri Lanka were below cause for concern (Subasinghe et al. 2012),

although the concentration of arsenic in the water was not determined and the proximity

of these reservoirs to potential sources of arsenic such as rice farms is not clear. We did

not evaluate arsenic or other heavy metals in biota from the Osa Province, but future

efforts should explore these contaminants.

5. It is also important to determine how fish acquire their pollutant load. Biomagnification

(increase of pesticide concentrations at higher trophic levels) does not appear to be the

primary mechanism by which fish acquire pesticide residues in the Osa Province. It may

be that fish absorb pesticides while in hot spots and eliminate or dilute these pesticides

when they leave these hot spots. This would explain why highly mobile species with

large home ranges, such as robalo, had lower contaminant levels than tilapia, which

generally have a more restricted home range, even when they were sampled in the same

location There may also be important ontogenetic shifts in life history behavior which

affect pesticide accumulation. For example, species like robalo may eat fewer

contaminated food items when they shift from a freshwater to marine phase.

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Table 1. Total number of fish and shellfish species collected 16-22 August (A) & 3-8 November 2011 (N) at each site. “M” indicates Fish from

Banco Pesces fish market in Palmar Norte that were purportedly from the HNTS.

Ocean Mangalar Rio Sierpe Rio Terraba Market Total

1 2 2 3 3 4 4 7 7 5 9 11 12 13 14 15 16 17 18 19 20 21 22 23 24 6 6 8 10 M

Family Species N A N A N A N A N A A A A A N N A A N N A A A N N A N A A A

Molluscs

Arcidae Anadara tuberculosa 8 10 15 21 16 13 83

Crustaceans

Amphipoda Scud 1 1

Cambaridae Crayfish 2 2

Palaemonidae Shrimp 15 1 13 29

Fish

Anablepidae Oxyzygonectes dovii 4 4

Ariidae Cathorops sp. 3 3

Carangidae Caranx sp. 1 1

Centropomidae Centropomus armatus 5 3 1 1 1 1 12

Centropomus medius 1 2 1 4

Centropomus nigrescens 3 2 4 9

Centropomus sp. 1 1

Centropomus unionensis 1 1

Centropomus viridis 3 1 4

Characidae Astyanax aeneus 1 9 8 5 23

Brycon behreae 1 1 1 3 2 4 12

Roeboides ilseae 1 2 5 8

Cichlidae Cichlid 1 1

Cryptoheros (Archocentrus) sajica 2 2

Oreochromis niloticus 4 1 4 1 3 13

Eleotridae Eleotris picta 2 2

Gobiomorus maculatus 1 2 2 5

Gobiidae Awaous transandeanus 2 2

Lutjanidae Lutjanus argentiventris 1 1 1 3

Lutjanus colorado 3 2 2 1 1 1 10

Lutjanus jordani 1 1

Poeciliidae Brachyrhaphis rhabdophora 54 54

Poecilia gillii 6 6

Sciaenidae Sciaenidae sp. 5 5

Total 9 5 10 15 21 16 13 6 1 8 1 6 72 1 1 6 1 1 1 1 7 20 18 1 5 4 3 8 29 3 301

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Table 2: Number of individual or composite samples (and the number of individuals in each sample) screened for pesticide residues using AXYS

Analytical Services, Ltd. method MLA-035 (MRES) and method MLA-028 (HR GC/MS).

Name (Spanish) Name (English) Species Waterbody Site Date MRES HR GC/MS

Piangua Mud cockle Anadara tuberculosa Mangrove 2 Aug. 1 (2)

2 Nov. 1 (6)

3 Aug. 1 (3)

4 Aug. 1 (3)

4 Nov. 1 (4)

Camarone Freshwater shrimp Palaemonidae Rio Sierpe 12 Aug. 1 (15)

22 Aug. 1 (15)

Machaca Sabalo Brycon behreae Rio Sierpe 14 Nov. 1 (1)

18 Nov. 1 (1)

19 Nov. 1 (1)

24 Nov. 1 (1)

Rio Térraba 6 Nov. 2 (1)

10 Aug. 1 (1)

Pargo colorado Red snapper Lutjanus colorado Ocean 1 Nov. 3 (1)

Rio Sierpe 17 Aug. 1 (1)

22 Aug. 1 (1)

Robalo aleta manchada Blackfin snook Centropomus medius Market M Aug. 1 (1)

Rio Sierpe 13 Aug. 1 (1)

Robalo chucumite Armed snook Centropomus armatus Mangrove 2 Aug. 3 (1)

7 Aug. 2 (1)

Market M Aug. 1 (1)

Rio Sierpe 23 Nov. 1 (1)

Rio Térraba 6 Nov. 1 (1)

10 Aug. 1 (1)

Robalo negro Black snook Centropomus nigrescens Ocean 1 Nov. 3 (1)

Rio Sierpe 24 Nov. 2 (1)

Rio Térraba 10 Aug. 3 (1)

Bagre Sea catfish Cathorops sp. Rio Térraba 6 Aug. 1 (3)

Tilapia Tilapia Oreochromis niloticus Rio Sierpe 15 Nov. 1 (1)

20 Aug. 1 (1)

21 Aug. 1 (1)

Rio Térraba 10 Aug. 3 (1)

Total

41 4

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Table 3: Analytes and typical detection limit for AXYS Analytical Services, Ltd. method MLA-

035 (MRES) and method MLA-028 (HR GC/MS; ng/g wet weight).

Analytes MRES HR

GC/MS

Organochlorines

Captan 0.60

Chlordane

Chlordane, oxy- 0.20 0.02

Chlordane, gamma (trans) 0.10 0.02

Chlordane, alpha (cis) 0.10 0.02

Nonachlor, trans- 0.10 0.02

Nonachlor, cis- 0.06 0.02

Chlorothalonil 0.04

Dacthal 0.04

4,4'-DDT 0.10 0.02

2,4'-DDD 0.10 0.02

4,4'-DDD 0.10 0.02

2,4'-DDE 0.20 0.02

4,4'-DDE 0.20 0.02

2,4'-DDT 0.10 0.02

Dieldrin 0.05 0.05

Aldrin 0.02 0.02

Endosulfan

alpha-Endosulphan 0.40 0.05

beta-Endosulphan 0.30 0.05

Endosulphan sulphate 0.30 0.05

Endrin 0.04 0.05

Endrin aldehyde 0.05

Endrin ketone 0.10 0.05

Hexachlorobenzene (HCB) 0.01 0.01

Heptachlor 0.02 0.02

Heptachlor epoxide 0.08 0.05

HCH, gamma (Lindane) 0.03 0.02

HCH, alpha 0.02 0.02

HCH, beta 0.03 0.02

HCH, delta 0.03 0.05

Mirex 0.01 0.02

Methoxychlor 0.60 0.10

Octachlorostyrene 0.02

Perthane 0.50

Quintozene 0.04

Tecnazene 0.05

Toxaphene, Technical 0.05

Triazines

Analytes MRES HR

GC/MS

Ametryn 0.05

Atrazine 0.90

Cyanazine 1.00

Desethylatrazine 0.10

Hexazinone 0.40

Metribuzin 0.50

Simazine 0.50

Organophosphates

Azinphos-methyl 2.00

Chlorpyriphos 0.08

Chlorpyriphos-methyl 0.04

Chlorpyriphos-oxon 0.20

Diazinon 0.40

Diazinon-oxon 0.70

Dimethoate 6.00

Disulfoton 0.80

Disulfoton sulfone 0.10

Ethion 0.10

Fenitrothion 0.20

Fonofos 0.04

Malathion 2.00

Methamidophos 2.00

Parathion-methyl 3.00

Parathion-ethyl 0.40

Phorate 0.50

Phosmet 0.30

Pirimiphos-methyl 0.08

Terbufos 0.20

Pyrethroids

Total-Permethrins 0.40

Total-Cypermethrins 2.00

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Table 4: Concentration of pesticides summed with their breakdown products (ng/g wet weight) in fish and shellfish from the Osa Province, Costa Rica. Red –

banned pesticides, orange – restricted use pesticides, blue – current use pesticides.

Site Date Species Sci. name No. Tissue TL(mm) Wt(g) % Lipid

Σ(A

ldrin

+

Die

ldrin

)

Σ(C

hlo

rd

an

e)

Σ(D

DT

)

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2 8/21/2011 Piangua Anadara tuberculosa 2 Whole clam - - 0.6 0.001 - - 0.011 - - 0.009 - - 0.518 - - - - - - - - - - -

2 11/5/2011 Piangua Anadara tuberculosa 6 Whole clam - - 0.36 - - - - - - - 0.001 - 0.049 - - - - - - - - - - -

3 8/17/2011 Piangua Anadara tuberculosa 3 Whole clam - - 0.52 0.001 - - - - 0.006 0.011 - - 0.069 - - - - - - - - - - -

4 8/16/2011 Piangua Anadara tuberculosa 3 Whole clam - - 0.56 - - - - - 0.002 0.003 - - 0.097 - - - - - - - - - - -

4 11/5/2011 Piangua Anadara tuberculosa 4 Whole clam - - 0.54 0.013 - - - - - - - - - - - - - - - - - - - -

12 8/22/2011 Camarone Shrimp 15 Whole shrimp - - 3.54 - - 0.005 - - - 0.024 0.005 - - - - - - - - - - - - -

22 8/21/2011 Camarone Shrimp 13 Whole shrimp - - 2.45 0.152 - 0.890 - - - 0.007 0.016 - - - - - - - - - - - - -

14 11/4/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 297 - 5.9 7.653 0.217 9.738 0.290 - 0.124 0.041 0.123 - 0.342 0.104 - - - 0.017 - - 0.007 - 0.294 -

18 11/4/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 350 - 7.53 0.075 - 1.127 - - 0.018 0.039 0.031 0.017 0.156 - - - - 0.054 - 0.208 - - - -

19 11/4/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 281 242.0 5.24 0.341 - 0.867 0.015 - - 0.025 0.028 0.082 0.469 - - - - - - - - - - -

24 11/4/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 350 392.0 4.08 0.068 0.005 0.417 0.014 - 0.007 0.030 0.009 0.089 0.139 - - - - 0.012 - - - - - -

6 11/5/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 327 - 2.17 0.007 0.005 0.108 0.011 - 0.004 0.016 0.019 0.747 0.129 - - - - 0.006 - 0.320 - - - -

6 11/5/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 298 - 3.11 0.048 0.014 0.165 0.001 - 0.029 0.028 0.008 0.736 0.406 - - - - 0.001 - 0.371 - - - -

10 8/20/2011 Machaca/Sabalo Brycon behreae 1 Skin-on filet 151 29.5 6.66 5.133 0.185 2.183 0.016 - 0.115 0.039 0.029 0.348 10.672 - - - 0.843 0.007 7.558 - - 0.053 - -

1 11/7/2011 Pargo colorado Lutjanus colorado 1 Skin-on filet 383 860.0 0.9 0.055 0.002 0.013 0.002 - - 0.005 0.007 0.200 0.204 - - - - 0.005 - - - - - -

1 11/7/2011 Pargo colorado Lutjanus colorado 1 Skin-on filet 402 800.0 0.48 0.021 - - 0.011 - - - 0.006 0.104 0.167 - - - - - - - - - - -

1 11/7/2011 Pargo colorado Lutjanus colorado 1 Skin-on filet 370 - 0.71 0.066 - 0.051 0.010 - - 0.006 0.005 0.140 0.268 - - - - - - - - - - -

17 8/18/2011 Pargo colorado Lutjanus colorado 1 Skin-on filet 248 - 0.67 0.017 0.005 - - - 0.015 0.004 0.003 0.036 0.126 - - - - - - - - - - -

22 8/17/2011 Pargo colorado Lutjanus colorado 1 Skin-on filet 168 - 0.76 0.007 - 0.169 - - 0.001 0.005 0.037 0.069 0.184 - - - - - - - - - - -

M 8/18/2011 Robalo aleta manchada Centropomus medius 1 Skin-on filet 384 - 0.69 0.004 0.011 0.043 0.014 - - 0.004 0.008 - 0.065 - - - - - - - - - - -

M 8/18/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 350 - 0.47 0.028 0.030 0.040 - - 0.012 0.002 0.001 - 0.408 - - - - 0.001 - - - - - -

13 8/19/2011 Robalo aleta manchada Centropomus medius 1 Skin-on filet 290 178.6 0.45 0.752 - 6.823 0.041 - - 0.006 0.130 - 0.050 - - - - - - - - - - -

23 11/4/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 304 323.0 1.76 0.018 0.007 0.488 0.001 - 0.002 0.021 0.033 - 0.021 - - - - - - - - - - -

24 11/4/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 434 637.0 1.18 0.002 - 0.292 - - - - 0.034 - 0.003 - - - - - - - - - - -

24 11/4/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 408 525.0 0.91 0.026 - 0.231 - - - 0.005 0.021 - - - - - - - - - - - - -

2 8/20/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 171 - 0.57 0.011 - 0.036 - - - 0.004 - 0.246 0.811 - - - - - - 0.062 - - - -

2 8/20/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 155 - 0.54 - - - 0.001 - 0.012 0.003 0.002 0.124 0.603 - - - - - - - - - - -

2 8/20/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 150 - 0.78 0.003 0.016 - - - 0.001 - 0.005 0.145 0.784 - - - - - - 0.067 - - - -

7 8/16/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 276 - 0.56 0.017 0.022 - - - 0.008 0.002 - - 0.215 - - - - - - - - - - -

7 8/16/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 331 413.9 0.62 0.031 - - - - - 0.001 0.003 0.035 0.119 - - - - - - - - - - -

6 11/5/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 313 - 0.74 0.008 - 0.001 - - 0.006 0.004 0.005 0.096 0.124 - - - - - - 0.114 - - - -

10 8/20/2011 Robalo chucumite Centropomus armatus 1 Skin-on filet 237 157.8 0.88 0.012 0.016 0.791 0.001 - - 0.005 0.037 0.126 0.554 - - - - - - - - - - -

10 8/20/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 451 650.0 0.7 0.106 - 5.804 0.347 - - 0.001 0.038 0.018 0.120 - - - - - - - - - - -

10 8/20/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 172 38.5 0.56 0.001 - 1.821 0.016 - - 0.004 0.032 - 0.334 - - - - - - - - - - -

10 8/20/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 160 31.0 0.81 0.005 - 0.722 - - - 0.005 0.021 - 0.156 - - - - - - - - - - -

1 11/7/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 632 2100.0 1.29 0.053 - 0.579 - - - - 0.019 - - - - - - - - - - - - -

1 11/7/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 523 990.0 0.93 0.031 - 0.105 - - 0.006 0.007 - 0.071 0.125 - - - - - - - - - - -

1 11/7/2011 Robalo negro Centropomus nigrescens 1 Skin-on filet 581 1600.0 0.27 0.029 - 0.224 - - - 0.005 0.024 0.074 0.046 - - - - - - - - - - -

6 8/21/2011 Bagre Cathorops sp. 3 Whole fish 63-85 1.9-4.53 2.29 0.078 - 0.324 0.004 - 0.002 0.020 0.163 3.530 3.586 - 0.200 5.718 - - 0.154 0.724 - 2.118 - -

15 11/3/2011 Tilapia Oreochromis urolepis 1 Skin-on filet 149 71.5 0.67 0.025 - 1.212 - - - 0.019 - - 0.118 - - - - - - 5.237 - - - -

20 8/19/2011 Tilapia Oreochromis urolepis 1 Skin-on filet 208 187.3 0.38 0.137 - 0.967 - - - 0.017 - - 0.114 - - - - - - - - - - -

21 8/19/2011 Tilapia Oreochromis urolepis 1 Skin-on filet 187 138.4 0.86 0.281 - 0.522 - - - - - - 0.036 - 0.089 - - - - - - - - -

10 8/20/2011 Tilapia Oreochromis urolepis 1 Skin-on filet 321 660.0 1.53 1.614 0.631 49.239 2.012 - 0.346 0.133 0.019 0.055 0.231 - - - - - 0.113 - - - - -

10 8/20/2011 Tilapia Oreochromis urolepis 1 Skin-on filet 223 271.2 1.25 0.689 0.279 20.970 0.579 0.022 0.115 0.039 0.016 - 0.216 - - - - - 1.066 - - - - 0.036

10 8/20/2011 Tilapia Oreochromis urolepis 1 Skin-on filet 184 143.9 0.82 0.515 0.145 15.323 0.644 - 0.071 0.070 - 0.027 0.138 - - - - - - - - - - -

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Table 5: Pesticide Reference Dose (RfD, mg/kg/d) and Cancer Slope Factor (CSF, [mg/kg/d]-1

) from the USEPA to

calculate consumption advisories. (* - a value of 1 is used when the RfD was not reported by the USEPA).

Class Pesticide CAS RfD CSF

Organochlorine Captan 133-06-2 0.13 0

Chlordane

Chlordane, oxy- 27304-13-8 0.0005 0.35

Chlordane, gamma(trans) 5103-74-2 0.0005 0.35

Chlordane, alpha(cis) 5103-71-9 0.0005 0.35

Nonachlor, trans- 39765-80-5 0.0005 0.35

Nonachlor, cis- 5103-73-1 0.0005 0.35

Chlorothalonil 1897-45-6 0.015 0

Dacthal 1861-32-1 0.01 0

4,4'-DDT 50-29-3 0.0005 0.34

2,4'-DDD 53-19-0 0.0005 0.34

4,4'-DDD 72-54-8 0.0005 0.34

2,4'-DDE 3424-82-6 0.0005 0.34

4,4'-DDE 72-55-9 0.0005 0.34

2,4'-DDT 789-02-6 0.0005 0.34

Dieldrin 60-57-1 0.00005 16

Aldrin 309-00-2 0.00003 16

Endosulfan

alpha-Endosulphan 959-98-8 0.006 0

beta-Endosulphan 33213-65-9 0.006 0

EndosulphanSulphate 1031-07-8 0.006 0

Endrin 72-20-8 0.0003 0

EndrinKetone 53494-70-5 0.0003 0

HCH,gamma (Lindane) 58-89-9 0.0003 1.3

HCH,alpha 319-84-6 1* 0

HCH,beta 319-85-7 1* 0

HCH,delta 319-86-8 1* 0

Heptachlor 76-44-8 0.0005 1.3

Heptachlor epoxide 1024-57-3 0.000013 9.1

Hexachlorobenzene 118-74-1 0.0008 1.6

Methoxychlor 72-43-5 1* 0

Mirex 2385-85-5 0.0002 0

Octachlorostyrene 29082-74-4 1* 0

Perthane 72-56-0 1* 0

Quintozene 82-68-8 0.003 0

Tecnazene 117-18-0 1* 0

Triazine Ametryn 834-12-8 0.009 0

Atrazine 1912-24-9 0.035 0

Cyanazine 21725-46-2 1* 0

Desethylatrazine 6190-65-4 0.035 0

Hexazinone 51235-04-2 1* 0

Metribuzin 21087-64-9 1* 0

Simazine 122-34-9 1* 0

Organophosphate Azinphos-Methyl 86-50-0 1* 0

Chlorpyriphos 2921-88-2 0.0003 0

Chlorpyriphos-methyl 5598-13-0 1* 0

Chlorpyriphos-oxon 5598-15-2 0.0003 0

Diazinon 333-41-5 0.0007 0

Diazinon-oxon 962-58-3 0.0007 0

Dimethoate 60-51-5 0.0002 0

Disulfoton 298-04-4 0.00004 0

Disulfoton sulfone 2497-06-5 0.00004 0

Ethion 563-12-2 0.0005 0

Fenitrothion 122-14-5 1* 0

Fonofos 944-22-9 1* 0

Malathion 121-75-5 1* 0

Methamidophos 10265-92-6 1* 0

Parathion-Ethyl 56-38-2 1* 0

Parathion-Methyl 298-00-0 1* 0

Phorate 298-02-2 1* 0

Phosmet 732-11-6 1* 0

Pirimiphos-Methyl 29232-93-7 0.01 0

Terbufos 13071-79-9 0.00002 0

Pyrethroid Permethrin 52645-53-1 0.05 0

Cypermethrin 52315-07-8 0.01 0

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36

Table 6: Fish consumption recommendations to avoid non-carcinogenic and carcinogenic health effects of pesticides.

Values are the recommended maximum number of 227 g (0.5 lbs.) meals per month of contaminanted fish or shellfish

for a 70 kg (154 lbs) person.

Species Waterbody Site Month No. Samples % Lipid

Non-

carcinogenic Carcinogenic

Piangua Mangrove 2 Aug. 1 0.60 60,854 3,088

2 Nov. 1 0.36 712,920 Inf.

3 Aug. 1 0.52 132,989 2,267

4 Aug. 1 0.56 392,479 12,685

4 Nov. 1 0.54 36,103 451

Camarone Rio Sierpe 12 Aug. 1 3.54 144,412 2,341

22 Aug. 1 2.45 1,912 34

Machaca/Sabalo Rio Sierpe 14 Nov. 1 5.90 50 0.7

18 Nov. 1 7.53 1,639 52

19 Nov. 1 5.24 1,028 16

24 Nov. 1 4.08 2,940 70

Rio Terraba 6 Nov. 2 2.64 1,859 143

10 Aug. 1 6.66 81 1.1

Pargo colorado Ocean 1 Nov. 3 0.70 5,942 122

Rio Sierpe 17 Aug. 1 0.67 5,638 225

22 Aug. 1 0.76 10,073 525

Robalo aleta manchada Market M Aug. 1 0.69 27,300 1,056

Robalo chucumite

M Aug. 1 0.47 5,526 161

Robalo aleta manchada Rio Sierpe 13 Aug. 1 0.45 315 6.5

Robalo chucumite

23 Nov. 1 1.76 6,048 191

Robalo negro

24 Nov. 2 1.04 9,806 296

Robalo chucumite Mangrove 2 Aug. 3 0.63 7,715 775

7 Aug. 2 0.59 10,145 220

Rio Terraba 6 Nov. 1 0.74 8,113 496

10 Aug. 1 0.88 3,484 198

Robalo negro

10 Aug. 3 0.69 1,356 61

Ocean 1 Nov. 3 0.83 5,767 131

Sea catfish Rio Terraba 6 Aug. 1 2.29 562 67

Tilapia Rio Sierpe 15 Nov. 1 0.67 898 111

20 Aug. 1 0.38 1,991 37

21 Aug. 1 0.86 1,405 20

Rio Terraba 10 Aug. 3 1.20 100 3.6

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37

Figure 1. Land use in the Rio Sierpe and lower Rio Grande de Terraba watersheds. Sampling sites indicated by white dots.

Page 39: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

38

Figure 3. Sampling locations for fish and shellfish in the Rio Grande de Térraba and Rio Sierpe, Osa Province, Costa Rica. Green outline

indicates boundary of the Humedal Nacional Térraba-Sierpe. Bullseyes indicate approximate locations of reported fish kills.

Page 40: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

39

Figure 4. Distribution of the observed pesticide load (ng/g wet weight) for each species, and for individuals as a

function of lipid content and length. Key: AA – Pargo, B- Bagre, C – Camarone, MM – Machaca, P – Piangua, R –

Robalo, T – Tilapia.

Species % Lipid Total Length

Org

anoch

lori

nes

Tri

azin

es

Org

anophosp

hat

es

Page 41: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

40

Figure 4 (Contiuned)

Pyre

thro

ids

All

Page 42: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

41

Figure 5: Concentration of pesticide residues summed with their breakdown products in skin-on fish filets,

whole clam or whole shrimp. Center of circle corresponds to the approximate location the sample was collected.

Verticle white box encloses different species from the same sampling location, horizontal white box encloses

samples from different dates (A – August, N – November). Red box indicates sample from the fish market in

Palmar Norte. Key: AA – Pargo, B- Bagre, C – Camarone, MM – Machaca, P – Piangua, R – Robalo, T – Tilapia.

Σ(Chlordane) Chlorothalonil

Σ(DDT) Dieldrin + Aldrin

Σ(Endosulfan) Σ(Endrin)

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42

Figure 5 (Continued)

Σ(Heptachlor) Hexachlorobenzene

Mirex

Chlorphyrifos

Diazinon

Rare (3 or fewer species and 2 or fewer sites)

Page 44: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

43

Figure 6. November 3-8, 2011 water physiochemistry

Temperature (°C) % DO saturation

pH

Conductivity (Ln[uS/cm])

Turbidity (Ln[NTU])

Page 45: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

44

Appendix Table 1 - Pesticide imports into Costa Rica for 2007, 2008 and 2009 (kg active ingredient) listed in

order of import in 2009. Pesticides in bold were screened in fish and shellfish as part of this study (n=21). (Data

adapted from Muñoz 2011).

2007 2008 2009

Total herbicide 3,926,534.92 4,347,735.45 3,357,808.64

Total fungicide 5,840,243.54 6,020,457.15 6,549,208.61

Total insecticide 2,118,757.36 2,094,302.68 1,681,637.37

Total fumigant 802,634.76 798,329.77 664,148.97

Total other 52,977.89 49,101.14 45,407.68

Pesticide (English) Use 2007 2008 2009 Mancozeb Fungicide 3,956,636.27 4,265,657.98 4,990,878.59

Glyphosate Herbicide 1,275,413.94 1,482,111.53 1,085,000.03

2,4-dichlorophenoxyacetic acid Herbicide 1,095,718.84 1,229,842.46 824,184.04

Paraquat Herbicide 350,192.84 370,870.56 457,735.40

Tridemorph Fungicide 490,235.01 388,387.41 336,245.59

Methyl bromide Fumigant 396,900.00 364,756.00 323,743.00

Diazinon Insecticide 202,426.00 379,306.00 313,867.40

Terbufos Insecticide 340,055.20 237,204.81 263,266.60

Metam sodium Fumigant 353,599.76 340,357.12 243,500.91

Ethoprophos Insecticide 339,791.95 365,456.88 229,042.77

Chlorothalonil Fungicide 287,999.90 289,125.55 212,297.18

Fenpropimorph Fungicide 86,996.90 64,574.40 158,189.68

Fosetil Fungicide 237,952.00 192,288.00 141,020.00

Pendimethalin Herbicide 209,567.00 104,733.32 139,111.49

Ametryn Herbicide 152,056.04 202,219.00 132,741.00

Oxamyl Insecticide 73,470.14 157,674.27 118,281.40

Diuron Herbicide 348,137.60 282,881.68 98,142.50

Bentazone Herbicide 21,219.20 42,438.40 96,928.00

Terbutryn Herbicide 72,090.00 150,465.00 89,300.00

Propineb Fungicide 80,675.10 100,808.90 87,245.20

Chlorpyrifos Insecticide 115,866.99 79,831.58 83,024.87

1,3-Dichloropropene Fumigant 37,907.50 69,857.05 82,187.49

Carbaryl Insecticide 80,576.20 101,367.44 79,824.60

Propanil Herbicide 42,089.28 73,546.38 76,114.50

Carbendazim Fungicide 110,405.45 107,008.97 69,878.30

Malathion Insecticide 66,317.40 55,222.08 64,661.70

Carbofuran Insecticide 101,785.58 134,290.13 64,527.95

Sulfur Insecticide 180,680.00 131,016.00 61,400.00

Cadusafos Insecticide 63,338.00 51,412.35 58,752.00

Dimethoate Insecticide 39,476.46 43,061.84 58,010.00

Fenamiphos Insecticide 203,300.90 42,640.70 55,946.80

Pyrimethanil Fungicide 49,656.00 40,747.20 54,996.00

Bromacil Herbicide 53,720.77 71,866.04 49,078.66

Cypermethrin Insecticide 37,842.05 30,189.00 45,817.50

Epoxiconazole Fungicide 25,267.18 23,811.88 45,759.75

Picloram Herbicide 36,454.38 24,869.84 45,596.33

Spiroxamine Fungicide 29,120.00 35,732.48 41,760.00

Ethephon Other 48,749.04 40,781.57 41,069.08

Methylarsonic acid or MSMA Herbicide 39,231.36 32,981.76 39,600.00

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45

Pesticide (English) Use 2007 2008 2009 Copper oxychloride Fungicide 27,096.98 47,754.46 30,830.71

Terbuthylazine Herbicide 34,500.50 27,630.00 30,130.00

Forato Insecticide 44,673.71 72,694.58 29,148.34

Acephate Insecticide 14,303.30 12,450.64 25,670.00

Difenoconazole Fungicide 51,830.54 30,537.56 24,128.00

Butachlor Herbicide 25,555.56 31,650.00 23,723.16

Metiram Fungicide 56,700.00 32,000.00 23,640.00

Ziram Fungicide 22,800.00 22,800.00 22,800.00

Pyraclostrobin Fungicide 10,824.15 10,298.34 22,185.70

Captan Fungicide 31,995.00 26,507.88 21,425.00

Tebuconazole Fungicide 15,690.08 25,169.75 20,570.06

MCPA Herbicide 6,517.20 13,770.40 17,330.00

Imazalil Fungicide 16,462.50 12,507.23 17,100.00

Thiophanate methyl Fungicide 24,363.09 33,857.99 16,990.98

Propiconazole Fungicide 4,654.35 9,104.57 16,903.50

Endosulfan Insecticide 42,625.11 50,282.91 16,303.50

Glufosinate Herbicide 11,684.75 6,020.10 16,028.70

Triclopyr Herbicide 18,064.96 17,292.19 15,917.73

Naled Insecticide 2,220.29 12,679.92 14,160.00

Benomyl Fungicide 8,370.00 18,375.00 13,850.00

Triadimefon Fungicide 11,175.46 12,455.55 13,322.73

Clomazone Herbicide 4,800.00 7,389.70 13,280.70

Quinclorac Herbicide 11,202.50 7,604.76 12,567.50

Dimethomorph Fungicide 10,095.15 11,022.70 12,091.25

Oxifluorfen Herbicide 10,954.58 20,090.20 11,784.10

Hexazinone Herbicide 23,039.67 13,206.00 11,767.20

Aluminum phosphide Insecticide 10,349.49 13,211.26 11,574.81

Folpet Fungicide 12,919.16 13,098.24 11,535.36

Metalaxyl Fungicide 11,301.94 12,860.70 10,509.33

Disulfoton Insecticide 2,472.80 5,440.00 10,386.40

Copper hydroxide Fungicide 36,558.96 73,390.00 10,375.00

Quintozene (PCNB) Fungicide 6,929.67 4,049.82 10,340.00

Prochloraz Fungicide 6,026.60 8,795.85 9,969.30

Thiocyclam Insecticide 7,743.03 16,705.48 9,183.20

Cimoxamil Fungicide 7,340.86 3,328.20 9,109.20

Bordeaux mixture Fungicide 4,000.00 5,337.50 8,875.00

Boscalid Fungicide 4,760.28 6,528.06 8,205.12

Zineb Fungicide 8,000.00 4,000.00 8,000.00

Diquat Herbicide 4,703.20 9,841.60 7,797.60

Kresoxim methyl Fungicide 7,245.00

Bitertanol Fungicide 13,080.00 10,575.60 7,122.00

Dazomet Fumigant 2,910.00 11,058.00 7,004.37

Profoxydim Herbicide 7,834.00 9,398.00 6,816.00

Triadimenol Fungicide 7,942.20 6,236.70 6,639.44

Chloropicrin Fumigant 11,317.50 12,301.60 6,629.12

Propamocarb Fungicide 7,364.40 9,585.27 6,590.42

Quizalofop Herbicide 2,969.42 4,053.12 6,354.56

Ferbam Fungicide 2,660.00 4,940.00 5,700.00

Chlorfenpyr Insecticide 1,440.00 2,976.24 5,316.00

Clethodim Herbicide 5,114.40 5,037.60 5,232.00

Potassium salts of fatty acids Insecticide 4,876.00 4,968.00 4,968.00

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Pesticide (English) Use 2007 2008 2009 Linuron Herbicide 3,960.00 8,848.00 4,940.00

Imazapic Herbicide 2,762.28 5,372.61 4,774.65

Metaldehyde Molusquicida 1570 1648 4704

Metaldehyde Insecticide 1,569.50 1,648.86 4,704.00

Methamidophos Insecticide 30,161.20 15,105.00 4,515.00

Permethrin Insecticide 5,723.68 5,514.69 4,471.80

Cyhalofop butyl Herbicide 2,413.44 2,880.00 4,446.00

Profenofos Insecticide 4,200.00

Tiram Fungicide 4,160.00 4,000.00 4,160.00

Imidacloprid Insecticide 8,238.57 4,936.85 3,907.40

Prothiofos Insecticide 5,042.50 3,680.00 3,500.00

Validamycin Fungicide 4,000.00 4,800.00 3,399.80

Chloroneb Fungicide 2,653.04 6,633.90 3,316.95

Azoxystrobin Fungicide 2,755.70 2,437.40 3,269.70

Fluazifop-P Herbicide 2,881.67 3,123.00 3,015.00

Dichlorvos Insecticide 10,858.00 3,228.00 2,988.00

Alachlor Herbicide 3,548.16 3,344.64 2,981.76

Oxadiazon Herbicide 191.52 2,462.40

Asulam Herbicide 4,400.00 2,400.00

Isoprothiolane Other 1,920.00 4,800.00 2,400.00

Atrazine Herbicide 15,115.00 27,799.30 2,280.00

Pymetrozine Insecticide 1,302.50 1,608.00 2,260.00

Pretilachlor Herbicide 2,050.00 1,040.00 2,250.00

Metsulfuron Herbicide 1,179.10 1,437.47 2,230.48

Aldicarb Insecticide 3,564.00 6,324.30 2,160.00

Anilophos Herbicide 2,868.40 6,932.68 2,102.16

Imazapyr Herbicide 10,247.85 16,930.99 2,093.55

Cartap Insecticide 4,845.00 1,845.00 2,000.00

Maneb Fungicide 1,004.80 1,920.00

Bispyribac sodium Herbicide 907.2 1,018.00 1,825.60

Flutolanil Fungicide 1,566.00 1,800.00 1,800.00

Bifenthrin Insecticide 2,473.14 742 1,752.70

Methomyl Insecticide 25,845.26 2,922.45 1,736.28

Thiabendazole Fungicide 3,360.00 2,672.80 1,713.20

Carbosulfan Insecticide 500 2,250.00 1,650.00

Spinosad Insecticide 2,958.72 1,414.80 1,647.36

Methiocarb Insecticide 531.95 1,291.45 1,629.20

Methiocarb Molusquicida 532 1291 1629

Benfuracarb Insecticide 2,100.00 2,400.00 1,600.00

Methyl Tolclofos Fungicide 1,600.50 872.5 1,597.50

Tiametoxan Other 1,117.25 1,867.50 1,546.10

Dodemorph Fungicide 2,040.00 1,536.00

Cyproconazole Fungicide 2,482.80 2,490.00 1,500.80

Etofenprox Insecticide 1,000.00 500 1,500.00

Sodium fluosilicate Insecticide 1,500.00 1,518.75 1,500.00

Streptomycin Fungicide 12,214.50 5,743.50 1,461.00

Carboxin Fungicide 848 2,200.00 1,305.00

Methyl parathion Insecticide 1,459.20 1,267.20

Propaquizafop+B210 Herbicide 369.6 277.2 1,190.40

Aminopyralid Herbicide 1,147.84

Methyl iodide Fumigant 1,084.08

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Pesticide (English) Use 2007 2008 2009 Fluoroxipyr Herbicide 5,608.68 1,760.24 970.25

Pencycuron Fungicide 375 750 937.5

Myclobutanil Fungicide 336 811.6 931.2

Iprodione Fungicide 1,600.96 8,531.90 925.2

Phoxim Insecticide 1,843.75 1,284.18 847.73

Dicofol Insecticide 902.8 828.8

Cypermethrin, Zeta- Insecticide 252 504 792

Ioxynil Herbicide 388.8 775.2

Fomesafen Herbicide 415 720

Trifloxystrobin Fungicide 2,484.00 1,609.70 703.7

Cyclosulfamuron Herbicide 1,049.66 699.78 699.78

Famoxadone Fungicide 385.72 841.05 678.6

Oxytetracycline Fungicide 2,464.93 950.35 639.3

TCMTB Fungicide 2,646.00 1,575.00 630

Cylfuthrin Insecticide 668.68 636 561.4

Iprovalicarb Fungicide 514.62 645.3 532.98

Cyhalothrin-lambda Insecticide 374.12 495.38 530.83

Pyrethrin Insecticide 192.71 386.61 520.65

Kasugamacina Fungicide 247.5 940.5 505.89

Deltamethryn Insecticide 476 906.75 502

Ethoxysulfuron Herbicide 122.4 218.8 475.2

abamectin Insecticide 985.67 112.99 473.7

Hydramethylnon Insecticide 418.16 380.55 468.3

Teflubenzuron Insecticide 934.2 816 468

Etradiazole Fungicide 544 183.3 412.79

Imazamox Herbicide 197.81 403.2

Fipronil Insecticide 361 546.4 403.2

Quaternary ammonium Fungicide 402 402 402

Novaluron Insecticide 235.12 522.1 379

Imazaquin Herbicide 225 375

Acibenzolar-s-methyl Other 400 1,120.00 350

Cyromazine Insecticide 301.5 460.5 349.5

Cypermethrin, Alpha- Insecticide 60.19 320 320

Thiacloprid Insecticide 644.9 2,287.50 320

Dichloran Fungicide 273

Haloxyfop Herbicide 541.92 866.88 264

Diflubenzuron Insecticide 130.82 0.11 261.62

Piperophos Herbicide 860 320 256

Carfentrazone Herbicide 241.92 336 240

Propargite Insecticide 240 240

Tetradifon Insecticide 80 240

Spiromesifen Insecticide 122.88 655.2 176.4

fenamidone Fungicide 64 128 128

Magnesium phosphide Insecticide 1,422.40 2,430.40 125.8

Indoxacarb Insecticide 136.31 216 121.5

Copper Sulfate Pentahydrate Fungicide 77.12 81.68 119.12

Pyrazosulfuron Herbicide 60 30 117

Clofentezine Insecticide 270 90 90

Sulfluramid Insecticide 100.5 157.98 90

Gentamicin Fungicide 120.16 60 86

Cypermethrin, Beta- Insecticide 80

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Pesticide (English) Use 2007 2008 2009 Hexythiazox Insecticide 40.5 40 80

Amitraz Insecticide 720 144 72

Fenoxaprop-P-ethyl Herbicide 130.5 417.51 55.62

Lufenuron Insecticide 112.26 32.4 53.64

Chlorflurenol Herbicide 48.25

Emamectin benzoate Insecticide 95.4 231.5 43.56

Daminozide Other 85 42.5 42.5

Cylfuthrin, Beta- Insecticide 80.61 52.5 40

Coumatetralil Rodenticida 23.44 141.75 23.06

Coumatetralil Insecticide 23.44 141.75 23.06

Nicosulfuron Herbicide 8.1

Difethialone Insecticide 6.25

Acetamiprid Insecticide 18.58 2.4

Flocoumafen Rodenticida 1.69 52.58 2.16

Flocoumafen Insecticide 1.69 52.58 2.16

Brodifacouma Rodenticida 1.41 31 0.95

Brodifacouma Insecticide 1.41 31 0.95

Bromadiolone Rodenticida 0.01 5 0.08

Bromadiolone Insecticide 0.01 5 0.08

Diphacinone Insecticide 0.32 0.05 0.05

Bromuconazole Fungicide 0.28

Bupirimate Fungicide 1.25

Dichlofluanid Fungicide 5,055.00 397.5

Fenbuconazole Fungicide 1,425.00

Potassium phosphite Fungicide 1,930.00

Hexaconazol Fungicide 0.94

Imibenconazole Fungicide 0.15

Iprobenfos Fungicide 6,240.00 2,880.00

Cupric oleate Fungicide 498.12 695.52

Copper hydroxide Fungicide 0.44

Oxycarboxin Fungicide 300

Tribasic copper sulfate Fungicide 23.76

Acetochlor Herbicide 13,824.00

Cyanamide Herbicide 499.2

Iodosulfuron methyl Herbicide 3.88

Isoxaflutole Herbicide 8.45 110.25

Metribuzin Herbicide 5,780.60 1,086.40

Norflurazon Herbicide 14.15

Simazine Herbicide 495.12 1,203.31

Tebuthiuron Herbicide 10

Trifloxysulfuron Herbicide 85.99 118.4

Benthiavalicarb Insecticide 0.1

Buprofezin Insecticide 750 250

Clotanidin Insecticide 2.4

Diafentiuron Insecticide 403 428.5

Fenitrothion Insecticide 1,267.50

Flufenoxuron Insecticide 96.36 280

Metoxifenozide Insecticide 668.16 307.2

Pirimicarb Insecticide 5

Pyriproxyfen Insecticide 200 100

Rotenone Insecticide 47.9

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Pesticide (English) Use 2007 2008 2009 Thiodicarb Insecticide 367.5 691

Triazophos Insecticide 18,612.00 20,080.00

Fentin Other 307.6

Cytokinin Other 9.57

Paclobutrazol Other 399 480

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Appendix Table 2. Legacy and current use pesticides used on rice in Costa Rica and other pesticides of interest or their breakdown

products based on literature, site visits and lab analyses. Pesticides in bold were screened as part of this study.

Chemical CAS number Chem class (15) Use (15) Ref

Restricted or Prohibited in Costa Rica (Year)

Propanil 709-98-8 Amide Herbicide 1,5,7,14

Cyhalofop butyl 122008-85-9 Aryloxyphenoxy propionic acid Herbicide 6

Benomyl 17804-35-2 Benzimidazole Fungicide 7 Carbendazim 10605-21-7 Benzimidazole Fungicide 14 Thiabendazole 148-79-8 Benzimidazole Fungicide 2,10 Diquat 2764-72-9 Bipyridylium Herbicide 12 Paraquat 1910-42-5 Bipyridylium Herbicide 1,7,12,13 Restricted (24 Dec 2007)

Aldicarb 116-06-3 Carbamate Insecticide 1,13 Restricted (02 Jan 2008) Carbofuran 1563-66-2 Carbamate Insecticide 2,10,13 Restricted (02 Jan 2008) Mancozeb 8018-01-7. Carbamate Fungicide 1,5,7,14

Methomyl 16752-77-5 Carbamate Insecticide 1,13 Restricted (27 Dec 2007) Butachlor 23184-66-9 Chloroacetanilide Herbicide 7

Pendimethalin 40487-42-1 Dinitroaniline Herbicide 1,9 Daminozide 1596-84-5 Hydrazide Growth regulator 13 Restricted (7 April 1992)

Boron 7440-42-8 Mineral Fertilizer 5 Cyhexatin 13121-70-5 Mineral (tin) Insecticide 13 Prohibited (13 April 1999)

Copper oxychloride 1332-65-6 Mineral Fungicide 5,14 Magnesium 7439-95-4 Mineral Fertilizer 5 Mercury 7439-97-6 Mineral Fungicide 9,13 Prohibited (13 April 1999)

Zinc 7440-66-6 Mineral Fertilizer 5 Bentazone 25057-89-0 Miscellaneous Herbicide 12 Clomazone 81777-89-1 Miscellaneous Herbicide 5 Imazalil 35554-44-0 Miscellaneous Fungicide 1,2,10 Imazapic 104098-48-8 Miscellaneous Herbicide 6 Imazapyr 81334-34-1 Miscellaneous Herbicide 6 Oxadiazon 19666-30-9 Miscellaneous Herbicide 1 Quinclorac 84087-01-4 Miscellaneous Herbicide 1,5,6 Tridemorph 81412-43-3 Morpholine Fungicide 1 Thiacloprid 111988-49-9 Neonicotinoid Insecticide 12 Thiamethoxam 153719-23-4 Neonicotinoid insecticide 5 Nitrofen 1836-75-5 Nitric chloride Herbicide 13 Prohibited (13 April 1999)

Methyl bromide 74-83-9 Organobromide Herbicide 1 2,4'-DDD 53-19-0 Organochlorine Breakdown product 8 Prohibited (13 April 1999)

2,4'-DDE 3424-82-6 Organochlorine Breakdown product 8 Prohibited (13 April 1999) 2,4'-DDT 789-02-6 Organochlorine Breakdown product 8 Prohibited (13 April 1999) 4,4'-DDD 72-54-8 Organochlorine Breakdown product 8 Prohibited (13 April 1999) 4,4'-DDE 72-55-9 Organochlorine Breakdown product 8 Prohibited (13 April 1999) 4,4'-DDT 50-29-3 Organochlorine Insecticide 1,3,8,13 Prohibited (13 April 1999) Aldrin 309-00-2 Organochlorine Insecticide 3,8,13 Prohibited (13 April 1999) Chlordane (Technical) 12789-03-6 Organochlorine Insecticide 3,8,13 Prohibited (13 April 1999) Chlordane, alpha(cis) 5103-71-9 Organochlorine Breakdown product 8 Prohibited (13 April 1999) Chlordane, gamma(trans) 5103-74-2 Organochlorine Breakdown product 8 Prohibited (13 April 1999) Chlordane, oxy- 27304-13-8 Organochlorine Breakdown product 8 Prohibited (13 April 1999)

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Chemical CAS number Chem class (15) Use (15) Ref

Restricted or Prohibited in Costa Rica (Year)

Chlordecone 143-50-0 Organochlorine Insecticide 3,13 Prohibited (13 April 1999) Chlordimeform 6164-98-3 Organochlorine Insecticide 3,13 Prohibited (13 April 1999) Chlorothalonil 1897-45-6 Organochlorine Fungicide 1,2,7,8,10

Dacthal* 1861-32-1 Organochlorine Herbicide 8 Dieldrin 60-57-1 Organochlorine Insecticide 1,3,8,13 Prohibited (13 April 1999)

Endosulfan 115-29-7 Organochlorine Insecticide 6,7,13 Prohibited for rice (9 Oct 2008) Endosulphan sulphate 1031-07-8 Organochlorine Breakdown product 8 Prohibited for rice (9 Oct 2008) Endosulphan, alpha- 959-98-8 Organochlorine Breakdown product 8 Prohibited for rice (9 Oct 2008) Endosulphan, beta- 33213-65-9 Organochlorine Breakdown product 8 Prohibited for rice (9 Oct 2008) Endrin 72-20-8 Organochlorine Insecticide 3,8,13 Prohibited (13 April 1999) Endrin ketone 53494-70-5 Organochlorine Breakdown product 8 Prohibited (13 April 1999) Glyphosate 1071-83-6 Organochlorine Herbicide 1,7

HCH, alpha 319-84-6 Organochlorine Insecticide 8 HCH, beta 319-85-7 Organochlorine Insecticide 8 HCH, delta 319-86-8 Organochlorine Insecticide 8 HCH, gamma-, Lindane 58-89-9 Organochlorine Insecticide 3,8,13 Prohibited (13 April 1999)

Heptachlor 76-44-8 Organochlorine Insecticide 1,3,8,13 Prohibited (13 April 1999) HeptachlorEpoxide 1024-57-3 Organochlorine Breakdown product 8 Prohibited (13 April 1999) Hexachlorobenzene 118-74-1 Organochlorine Fungicide 1,8

Methoxychlor 72-43-5 Organochlorine Insecticide 8,9 Mirex/Declorano 2385-85-5 Organochlorine Insecticide 8,13 Prohibited (13 April 1999)

Nonachlor, cis- 5103-73-1 Organochlorine Breakdown product 8 Prohibited (13 April 1999) Nonachlor, trans- 39765-80-5 Organochlorine Breakdown product 8 Prohibited (13 April 1999) Octachlorostyrene 29082-74-4 Organochlorine Breakdown product 8,9

Organochlorines Various Organochlorine Various 13 Prohibited for cattle (3 Oct 1988) Pentachlorophenol 87-86-5 Organochlorine Insecticide 3,13 Prohibited (13 April 1999) Perthane* (ethylan) 72-56-0 Organochlorine Insecticide 8

Quintozene (PCNB) 82-68-8 Organochlorine Fungicide 8

Tecnazene 117-18-0 Organochlorine Fungicide, Plant growth regulator 8

Toxaphene 8001-35-2 Organochlorine Insecticide 1,3,13 Prohibited (13 April 1999) Anilofos 64249-01-0 Organophosphate Herbicide 5

Azinphos-Methyl 86-50-0 Organophosphate Insecticide 8 Cadusafos 95465-99-9 Organophosphate insecticide 1,2,10

Chlorpyriphos 2921-88-2 Organophosphate Insecticide 1,2,7,8,10,1

3 Restricted (27 Dec 2007) Chlorpyriphos-Methyl* 5598-13-0 Organophosphate Breakdown product 8,12 Restricted (27 Dec 2007) Chlorpyriphos-Oxon* 5598-15-2 Organophosphate Breakdown product 8 Restricted (27 Dec 2007) Diazinon 333-41-5 Organophosphate Insecticide 2,8,10,14

Diazinon-Oxon 962-58-3 Organophosphate Breakdown product 8 Dimethoate* 60-51-5 Organophosphate Insecticide 8,14 Disulfoton* 298-04-4 Organophosphate Insecticide 8 DisulfotonSulfone* 2497-06-5. Organophosphate Breakdown product 8 Edifenphos 17109-49-8 Organophosphate Fungicide 1 Ethephon 16672-87-0 Organophosphate Growth regulator 13 Prohibited for coffee (13 April 1999)

Ethion* 563-12-2 Organophosphate Insecticide 8 Ethoprophos 13194-48-4 Organophosphate Insecticide 2,10,13 Restricted (26 Dec 2007)

Fenamiphos 22224-92-6 Organophosphate Nematocide 10

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Chemical CAS number Chem class (15) Use (15) Ref

Restricted or Prohibited in Costa Rica (Year)

Fenitrothion* 122-14-5 Organophosphate Insecticide 8 Fonofos 944-22-9 Organophosphate Insecticide 8 Malathion 121-75-5 Organophosphate Insecticide 1,8 Methamidophos 10265-92-6 Organophosphate Insecticide 1,7,8 Methylparathion 298-00-0 Organophosphate Insecticide 1,8,13 Restricted (26 Dec 2007)

Monocrotofos 6923-22-4 Organophosphate Insecticide 7,13 Prohibited (27 Dec 2007) Parathion-Ethyl* 56-38-2 Organophosphate insecticide 1

Phorate* 298-02-2 Organophosphate Insecticide 8 Phosmet* 732-11-6 Organophosphate Insecticide 8 Pirimiphos-Methyl* 29232-93-7 Organophosphate Insecticide 8 Profenophos 41198-08-7 Organophosphate insecticide 5 SulfoTEPP 3689-24-5 Organophosphate Insecticide, Breakdown product 11 Terbufos 13071-79-9 Organophosphate Insecticide 1,2,8,10,13 Restricted (27 Dec 2007)

Triazophos 24017-47-8 Organophosphate Insecticide 6, 14 Paraffinic oil 64742-46-7 Petroleum Insecticide, Surfactant 7

Dinoseb 88-85-7 Phenol Herbicide, Insecticide, Fungicide 13 Prohibited (13 April 1999)

Mecoprop 7085-19-0 Phenoxy Herbicide 1 2,4,5- trichlorophenoxyacetic

acid 93-76-5 Phenoxyacetic acid Herbicide 1,13 Prohibited (22 April 1987) 2,4-dichlorophenoxyacetic acid 94-75-7 Phenoxyacetic acid Herbicide 1,7 Prohibited (13 April 1999) Dichlorprop 7547-66-2 Phenoxyacetic acid Herbicide 13 Prohibited (22 Nov 2004) MCPA 94-74-6 Phenoxyacetic acid Herbicide 7

Aluminum phosphide 20859-73-8 Phosphide Fungicide 13 Restricted (12 Dec 2007) Captafol .2425-06-1 Phthalamide Fungicide 13 Prohibited (13 April 1999) Captan* 133-06-2 Phthalamide Fungicide 8,13 Prohibited (13 April 1999) Octylphenoxypolyethoxyethanol 9036-19-5 Polyalkyloxy compound Surfactant 5

Fipronil 120068-37-3 Pyrazole Insecticide 12 Cyhalothrin, Lambda 91465-08-6 Pyrethroid Insecticide 5,8,12 Cypermethrin 52315-07-8 Pyrethroid Insecticide 1,7,8,12 Deltamethrin 52918-63-5 Pyrethroid Insecticide 1,6,8 Etofenprox 80844-07-1 Pyrethroid Insecticide 5 Permethrin 52645-53-1 Pyrethroid Insecticide 8 Azoxystrobin 131860-33-8 Strobin Fungicide 12 Trifloxystrobin 141517-21-7 Strobin Fungicide 12 Metsulfuron-methyl 74223-64-6 Sulfonylurea Herbicide 7 Ametryn 834-12-8 Triazine Herbicide 1,2,8,10 Atrazine 1912-24-9 Triazine Herbicide 1,7,8 Atrazine, desethyl- 6190-65-4 Triazine Breakdown product 8 Cyanazine* 21725-46-2 Triazine Herbicide 8 Hexazinone* 51235-04-2 Triazinone Herbicide 8 Metribuzin* 21087-64-9 Triazole Herbicide 8 Propiconazole 60207-90-1 Triazole Fungicide 1,2,5,10 Simazine 122-34-9 Triazole Herbicide 8 Tebuconazole 107534-96-3 Triazole Fungicide 5, 14 Triadimenol 55219-65-3 Triazole Fungicide 5, 14 Diflubenzuron 35367-38-5 Urea Insecticide 12 Diuron 330-54-1 Urea Herbicide 7

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Chemical CAS number Chem class (15) Use (15) Ref

Restricted or Prohibited in Costa Rica (Year)

Calcium cyanide (Cianoga [Spanish]) Cyanogas [English])

592-01-8 Cyanide Fungicide, Rodenticide 13 Prohibited (22 Oct 1960)

Agriful

Fertilizer 6 Fertilizer

Fertilizer 7

Kaytar

pH buffer 5,14 Silver citrate 126-45-4

? 14

Ref Title

1 (Castillo et al. 1997) Castillo, L. E., De La Cruz, E. & Ruepert, C. (1997). Ecotoxicology and pesticides in tropical aquatic ecosystems of Central America. Environmental Toxicology and Chemistry 16, 41-51.

2 (Castillo et al. 2006) Castillo, L. E., Martínez, E., Ruepert, C., Savage, C., Gilek, M., Pinnock, M. & Solis, E. (2006). Water quality and macroinvertebrate community response following pesticide applications in a banana plantation, limon, Costa Rica. Science of the Total Environment 367, 418-432.

3 Castillo, L. E. (no year) Persistent Organic Pesticides in Costa Rica, http://www.chem.unep.ch/pops/pops_inc/proceedings/cartagena/CASTILLO.html 4 World Health Organization (2009). The WHO Recommended Classification of Pesticides by Hazard and Guidelines to Classification. ISBN 978 92 4 154796 3

(http://www.who.int/ipcs/publications/pesticides_hazard_2009.pdf) 5 Rainforest Alliance - "Agroquemicos de Arroz Primer Siembra 2009 - Herman Fabrega” 6 Bottle or label found in Rice Paddy by SWRC scientists - August & November 2011 7 Recommendations for rice in Costa Rica from http://www.crystal-chemical.com/ (accessed 2011) 8 US EPA (Dec. 2007) Method 1699: Pesticides in Water, Soil, Sediment, Biosolids, and Tissue by HRGC/HRMS (EPA-821-R-08-001) 9 US EPA PBT/TRI priority 10 (Castillo et al. 2000) Castillo, L.E., Ruepert, C. and Solis, E. (2000) Pesticide residues in the aquatic environment of banana plantation areas in the North Atlantic Zone of

Costa Rica. Environmental Toxicology and Chemistry 19, 1942–1950. 11 Sulfotep is a stable breakdown product of Diazinon, and may also be used a pesticide 12 FAO/WHO Food Standards, Pesticide Residues in Food and Feed - Commodity Details - GC 0649 - Rice

(http://www.codexalimentarius.net/pestres/data/commodities/details.html?id=158) 13 PLAGUICIDAS PROHIBIDOS Y RESTRINGIDOS EN COSTA RICA (22/03/11) 14 Pesticides observed in storage shed on rice farm, Nov. 2011 15 PAN (Pesticide Action Network) www.pesticideinfo.org (June 27, 2012)

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Appendix Table 3: Analysis of covariance (ANCOVA) to test for effect of species, lipid content

and total length (TL) on pesticide concentration. Model tested: Log10(Sum[Pesticide]+0.0001) =

Species + TL + Lipid + Species * TL + Species * Lipid + TL * Lipid + Species * TL * Lipid

ORGANOCHLORINES Df Sum Sq Mean Sq F value Pr(>F)

Species 4 8.418 2.1045 7.879 0.000424

TL 1 0.165 0.1649 0.618 0.440331

Lipid 1 1.846 1.8464 6.913 0.015318

Species*TL 3 2.411 0.8036 3.009 0.051996

Species*Lipid 3 0.572 0.1908 0.714 0.553851

TL*Lipid 1 0.019 0.0185 0.069 0.794762

Species*TL*Lipid 3 0.161 0.0538 0.201 0.894294

Residuals 22 5.876 0.2671

ORGANOPHOSPHATES Df Sum Sq Mean Sq F value Pr(>F)

Species 4 33.02 8.254 3.271 0.0301

TL 1 0.39 0.393 0.156 0.6971

Lipid 1 0.85 0.849 0.336 0.5678

Species*TL 3 0.95 0.315 0.125 0.9443

Species*Lipid 3 2.48 0.828 0.328 0.805

TL*Lipid 1 0.1 0.099 0.039 0.8451

Species*TL*Lipid 3 5.9 1.967 0.78 0.5179

Residuals 22 55.51 2.523

PYRETHROIDS Df Sum Sq Mean Sq F value Pr(>F)

Species 4 28.274 7.069 31.467 8.19E-09

TL 1 0.022 0.022 0.098 0.7569

Lipid 1 5.408 5.408 24.074 6.61E-05

Species*TL 3 25.052 8.351 37.174 8.66E-09

Species*Lipid 3 2.84 0.947 4.215 0.0169

TL*Lipid 1 0.843 0.843 3.752 0.0657

Species*TL*Lipid 3 3.058 1.019 4.538 0.0127

Residuals 22 4.942 0.225

TRIAZINE Df Sum Sq Mean Sq F value Pr(>F)

Species 4 22.488 5.622 18.855 7.41e-07

TL 1 0.03 0.03 0.1 0.755

Lipid 1 0.002 0.002 0.006 0.939

Species*TL 3 0.49 0.163 0.548 0.655

Species*Lipid 3 0.106 0.035 0.118 0.948

TL*Lipid 1 0.008 0.008 0.026 0.875

Species*TL*Lipid 3 0.264 0.088 0.295 0.828

Residuals 22 6.56 0.298

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Appendix Table 4: Pesiticide residue concentration of individual fish filet or composited whole animals (ng/g wet weight). Zero values were below

the detection limit. Watershed Rio Sierpe Rio Sierpe Rio Sierpe Rio Sierpe Rio Térraba Rio Térraba Rio Térraba Ocean Ocean Ocean

Map# 14 18 19 24 6 6 10 1 1 1

Date 11/4/2011 11/4/2011 11/4/2011 11/4/2011 11/5/2011 11/5/2011 8/20/2011 11/7/2011 11/7/2011 11/7/2011

Name Machaca/Sabalo Machaca/Sabalo Machaca/Sabalo Machaca/Sabalo Machaca/Sabalo Machaca/Sabalo Machaca/Sabalo Pargo colorado Pargo colorado Pargo colorado

Species Brycon behreae Brycon behreae Brycon behreae Brycon behreae Brycon behreae Brycon behreae Brycon behreae Lutjanus colorado Lutjanus colorado Lutjanus colorado

No. in sample 1 1 1 1 1 1 1 1 1 1

Tissue Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet

TL (mm) 297 350 281 350 327 298 151 383 402 370

Wt (g) - - 242.0 392.0 - - 29.5 860.0 800.0 -

% Lipid 5.9 7.53 5.24 4.08 2.17 3.11 6.66 0.9 0.48 0.71

Tecnazene 117-18-0 0 0 0 0 0 0 0 0 0 0

Hexachlorobenzene 118-74-1 0.041 0.039 0.025 0.03 0.016 0.028 0.039 0.005 0 0.006

Quintozene 82-68-8 0 0 0 0 0 0 0 0 0 0

Heptachlor 76-44-8 0.018 0 0 0 0.001 0.004 0.062 0 0 0

HCH, alpha 319-84-6 0 0 0 0 0 0 0 0 0 0

HCH, gamma 58-89-9 0 0 0 0 0 0 0 0 0 0

HCH, beta 319-85-7 0 0 0 0 0 0 0 0 0 0

HCH, delta 319-86-8 0 0 0 0 0 0 0 0 0 0

Chlorothalonil * 1897-45-6 0.017 0.054 0 0.012 0.006 0.001 0.007 0.005 0 0

Aldrin 309-00-2 0 0 0 0 0 0 0 0 0 0

Dacthal * 1861-32-1 0 0 0 0 0 0 0 0 0 0

Octachlorostyrene 29082-74-4 0.007 0 0 0 0 0 0 0 0 0

Chlordane, oxy- 27304-13-8 0.007 0 0 0 0 0.006 0.016 0.002 0 0

Heptachlor Epoxide 1024-57-3 0.106 0.018 0 0.007 0.003 0.025 0.053 0 0 0

Chlordane, gamma (trans) 5103-74-2 0.112 0 0 0 0 0.008 0.129 0 0 0

Chlordane, alpha (cis) 5103-71-9 0.022 0 0 0 0 0 0.04 0 0 0

Nonachlor, trans- 39765-80-5 0.041 0 0 0 0 0 0 0 0 0

Nonachlor, cis- 5103-73-1 0.035 0 0 0.005 0.005 0 0 0 0 0

alpha-Endosulphan 959-98-8 0.232 0.088 0.198 0.139 0.12 0.143 0.708 0.036 0.158 0.149

beta-Endosulphan 33213-65-9 0.009 0.037 0.195 0 0.009 0.158 9.378 0.005 0 0.119

Dieldrin 60-57-1 7.653 0.075 0.341 0.068 0.007 0.048 5.133 0.055 0.021 0.066

2,4'-DDD 53-19-0 0.246 0.005 0.013 0.026 0 0 0.097 0 0 0

4,4'-DDD 72-54-8 2.028 0.12 0.128 0.096 0.008 0.033 0.588 0 0 0

2,4'-DDE 3424-82-6 0.047 0 0 0 0 0 0 0 0 0

4,4'-DDE 72-55-9 6.195 0.965 0.603 0.273 0.1 0.105 0.985 0.013 0 0.051

2,4'-DDT 789-02-6 0.079 0 0 0 0 0 0.024 0 0 0

4,4'-DDT 50-29-3 1.143 0.037 0.123 0.022 0 0.027 0.489 0 0 0

Captan * 133-06-2 0 0 0 0 0 0 0.843 0 0 0

Perthane * 72-56-0 0 0 0 0 0 0 0 0 0 0

Endrin 72-20-8 0.273 0 0.015 0.014 0.011 0.001 0.016 0.002 0.011 0.01

Endosulphan Sulphate 1031-07-8 0.101 0.031 0.076 0 0 0.105 0.586 0.163 0.009 0

Mirex 2385-85-5 0.123 0.031 0.028 0.009 0.019 0.008 0.029 0.007 0.006 0.005

Methoxychlor 72-43-5 0 0 0 0 0 0 0 0 0 0

Endrin Ketone 53494-70-5 0.017 0 0 0 0 0 0 0 0 0

Desethylatrazine 6190-65-4 0 0 0 0 0 0 0 0 0 0

Simazine 122-34-9 0 0 0 0 0 0 0 0 0 0

Atrazine 1912-24-9 0 0 0 0 0 0 0 0 0 0

Ametryn * 834-12-8 0 0 0 0 0 0 0 0 0 0

Metribuzin * 21087-64-9 0 0 0 0 0 0 0 0 0 0

Cyanazine * 21725-46-2 0 0 0 0 0 0 0 0 0 0

Hexazinone * 51235-04-2 0 0 0 0 0 0 0 0 0 0

Methamidophos * 10265-92-6 0 0 0 0 0 0 0 0 0 0

Phorate * 298-02-2 0 0 0 0 0 0 0 0 0 0

Terbufos * 13071-79-9 0.104 0 0 0 0 0 0 0 0 0

Diazinon-Oxon 962-58-3 0 0 0 0 0 0 0 0 0 0

Diazinon 333-41-5 0 0.208 0 0 0.32 0.371 0 0 0 0

Disulfoton * 298-04-4 0 0 0 0 0 0 0 0 0 0

Fonofos 944-22-9 0 0 0 0 0 0 0 0 0 0

Dimethoate * 60-51-5 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Methyl * 5598-13-0 0 0 0 0 0 0 0 0 0 0

Parathion-Methyl * 298-00-0 0 0 0 0 0 0 0 0 0 0

Pirimiphos-Methyl * 29232-93-7 0.294 0 0 0 0 0 0 0 0 0

Chlorpyriphos * 2921-88-2 0 0.017 0.082 0.089 0.747 0.736 0.348 0.2 0.104 0.14

Fenitrothion * 122-14-5 0 0 0 0 0 0 0 0 0 0

Malathion * 121-75-5 0 0 0 0 0 0 0 0 0 0

Parathion-Ethyl * 56-38-2 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Oxon * 5598-15-2 0 0 0 0 0 0 0 0 0 0

Disulfoton Sulfone * 2497-06-5 0 0 0 0 0 0 0 0 0 0

Ethion * 563-12-2 0 0 0 0 0 0 0 0 0 0

Phosmet * 732-11-6 0 0 0 0 0 0 0 0 0 0

Azinphos-Methyl 86-50-0 0 0 0 0 0 0 0 0 0 0

Permethrin 52645-53-1 0 0 0 0 0 0 0.053 0 0 0

Cypermethrin 52315-07-8 0 0 0 0 0 0 7.558 0 0 0

Page 57: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

56

Appendix Table 4 (Continued) Watershed Rio Sierpe Rio Sierpe Market Market Rio Sierpe Rio Sierpe Rio Sierpe Rio Sierpe Mangalar Mangalar

Map# 17 22 M M 13 23 24 24 2 2

Date 8/18/2011 8/17/2011 8/18/2011 8/18/2011 8/19/2011 11/4/2011 11/4/2011 11/4/2011 8/20/2011 8/20/2011

Name

Pargo colorado Pargo colorado Robalo aleta manchada/ Robalo chucumite

Robalo aleta

manchada/

Robalo

chucumite Robalo negro Robalo negro

Robalo

chucumite

Robalo

chucumite

Species

Lutjanus colorado Lutjanus colorado Centropomus medius Centropomus armatus

Centropomus

medius

Centropomus

armatus

Centropomus

nigrescens

Centropomus

nigrescens

Centropomus

armatus

Centropomus

armatus

No. fish in sample 1 1 1 1 1 1 1 1 1 1

Tissue Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet

TL (mm) 248 168 384 350 290 304 434 408 171 155

Wt (g) - - - - 178.6 323.0 637.0 525.0 - -

% Lipid 0.67 0.76 0.69 0.47 0.45 1.76 1.18 0.91 0.57 0.54

Tecnazene 117-18-0 0 0 0 0 0 0 0 0 0 0

Hexachlorobenzene 118-74-1 0.004 0.005 0.004 0.002 0.006 0.021 0 0.005 0.004 0.003

Quintozene 82-68-8 0 0 0 0 0 0 0 0 0 0

Heptachlor 76-44-8 0 0.001 0 0 0 0.002 0 0 0 0

HCH, alpha 319-84-6 0 0 0 0 0 0 0 0 0 0

HCH, gamma 58-89-9 0 0 0 0 0 0 0 0 0 0

HCH, beta 319-85-7 0 0 0 0 0 0 0 0 0 0

HCH, delta 319-86-8 0 0 0 0 0 0 0 0 0 0

Chlorothalonil * 1897-45-6 0 0 0 0.001 0 0 0 0 0 0

Aldrin 309-00-2 0 0 0.004 0 0.026 0 0.002 0 0.002 0

Dacthal * 1861-32-1 0 0 0 0 0 0 0 0 0 0

Octachlorostyrene 29082-74-4 0 0 0 0 0 0 0 0 0 0

Chlordane, oxy- 27304-13-8 0 0 0.011 0 0 0 0 0 0 0

Heptachlor Epoxide 1024-57-3 0.015 0 0 0.012 0 0 0 0 0 0.012

Chlordane, gamma (trans) 5103-74-2 0 0 0 0 0 0 0 0 0 0

Chlordane, alpha (cis) 5103-71-9 0 0 0 0 0 0 0 0 0 0

Nonachlor, trans- 39765-80-5 0 0 0 0 0 0.007 0 0 0 0

Nonachlor, cis- 5103-73-1 0.005 0 0 0.03 0 0 0 0 0 0

alpha-Endosulphan 959-98-8 0.068 0.184 0 0.027 0.039 0 0 0 0.002 0.022

beta-Endosulphan 33213-65-9 0.019 0 0.065 0.043 0.011 0 0 0 0.244 0.1

Dieldrin 60-57-1 0.017 0.007 0 0.028 0.726 0.018 0 0.026 0.009 0

2,4'-DDD 53-19-0 0 0 0 0 0.011 0 0 0 0 0

4,4'-DDD 72-54-8 0 0 0 0.007 0.563 0.037 0.009 0.005 0 0

2,4'-DDE 3424-82-6 0 0 0 0 0.001 0 0 0 0 0

4,4'-DDE 72-55-9 0 0.169 0.043 0.033 5.826 0.44 0.279 0.226 0.036 0

2,4'-DDT 789-02-6 0 0 0 0 0 0 0 0 0 0

4,4'-DDT 50-29-3 0 0 0 0 0.422 0.011 0.004 0 0 0

Captan * 133-06-2 0 0 0 0 0 0 0 0 0 0

Perthane * 72-56-0 0 0 0 0 0 0 0 0 0 0

Endrin 72-20-8 0 0 0.014 0 0.041 0.001 0 0 0 0.001

Endosulphan Sulphate 1031-07-8 0.039 0 0 0.338 0 0.021 0.003 0 0.565 0.481

Mirex 2385-85-5 0.003 0.037 0.008 0.001 0.13 0.033 0.034 0.021 0 0.002

Methoxychlor 72-43-5 0 0 0 0 0 0 0 0 0 0

Endrin Ketone 53494-70-5 0 0 0 0 0 0 0 0 0 0

Desethylatrazine 6190-65-4 0 0 0 0 0 0 0 0 0 0

Simazine 122-34-9 0 0 0 0 0 0 0 0 0 0

Atrazine 1912-24-9 0 0 0 0 0 0 0 0 0 0

Ametryn * 834-12-8 0 0 0 0 0 0 0 0 0 0

Metribuzin * 21087-64-9 0 0 0 0 0 0 0 0 0 0

Cyanazine * 21725-46-2 0 0 0 0 0 0 0 0 0 0

Hexazinone * 51235-04-2 0 0 0 0 0 0 0 0 0 0

Methamidophos * 10265-92-6 0 0 0 0 0 0 0 0 0 0

Phorate * 298-02-2 0 0 0 0 0 0 0 0 0 0

Terbufos * 13071-79-9 0 0 0 0 0 0 0 0 0 0

Diazinon-Oxon 962-58-3 0 0 0 0 0 0 0 0 0 0

Diazinon 333-41-5 0 0 0 0 0 0 0 0 0.062 0

Disulfoton * 298-04-4 0 0 0 0 0 0 0 0 0 0

Fonofos 944-22-9 0 0 0 0 0 0 0 0 0 0

Dimethoate * 60-51-5 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Methyl * 5598-13-0 0 0 0 0 0 0 0 0 0 0

Parathion-Methyl * 298-00-0 0 0 0 0 0 0 0 0 0 0

Pirimiphos-Methyl * 29232-93-7 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos * 2921-88-2 0.036 0.069 0 0 0 0 0 0 0.246 0.124

Fenitrothion * 122-14-5 0 0 0 0 0 0 0 0 0 0

Malathion * 121-75-5 0 0 0 0 0 0 0 0 0 0

Parathion-Ethyl * 56-38-2 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Oxon * 5598-15-2 0 0 0 0 0 0 0 0 0 0

Disulfoton Sulfone * 2497-06-5 0 0 0 0 0 0 0 0 0 0

Ethion * 563-12-2 0 0 0 0 0 0 0 0 0 0

Phosmet * 732-11-6 0 0 0 0 0 0 0 0 0 0

Azinphos-Methyl 86-50-0 0 0 0 0 0 0 0 0 0 0

Permethrin 52645-53-1 0 0 0 0 0 0 0 0 0 0

Cypermethrin 52315-07-8 0 0 0 0 0 0 0 0 0 0

Page 58: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

57

Appendix Table 4 (Continued)

Watershed Mangalar Mangalar Mangalar Rio Térraba Rio Térraba Rio Térraba Rio Térraba Rio Térraba Ocean Ocean

Map# 2 7 7 6 10 10 10 10 1 1

Date 8/20/2011 8/16/2011 8/16/2011 11/5/2011 8/20/2011 8/20/2011 8/20/2011 8/20/2011 11/7/2011 11/7/2011

Name

Robalo chucumite/ Robalo chucumitek Robalo chucumite/ Robalo chucumite/

Robalo

chucumite/ Robalo negro Robalo negro Robalo negro Robalo negro Robalo negro

Species

Centropomus armatus Centropomus armatus Centropomus armatus Centropomus armatus

Centropomus

armatus

Centropomus

nigrescens

Centropomus

nigrescens

Centropomus

nigrescens

Centropomus

nigrescens

Centropomus

nigrescens

No. fish in sample 1 1 1 1 1 1 1 1 1 1

Tissue Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet

TL (mm) 150 276 331 313 237 451 172 160 632 523

Wt (g) - - 413.9 - 157.8 650.0 38.5 31.0 2100.0 990.0

% Lipid 0.78 0.56 0.62 0.74 0.88 0.70 0.56 0.81 1.29 0.93

Tecnazene 117-18-0 0 0 0 0 0 0 0 0 0 0

Hexachlorobenzene 118-74-1 0 0.002 0.001 0.004 0.005 0.001 0.004 0.005 0 0.007

Quintozene 82-68-8 0 0 0 0 0 0 0 0 0 0

Heptachlor 76-44-8 0.001 0 0 0 0 0 0 0 0 0.006

HCH, alpha 319-84-6 0 0 0 0 0 0 0 0 0 0

HCH, gamma 58-89-9 0 0 0 0 0 0 0 0 0 0

HCH, beta 319-85-7 0 0 0 0 0 0 0 0 0 0

HCH, delta 319-86-8 0 0 0 0 0 0 0 0 0 0

Chlorothalonil * 1897-45-6 0 0 0 0 0 0 0 0 0 0

Aldrin 309-00-2 0 0.003 0 0 0.01 0 0 0 0 0

Dacthal * 1861-32-1 0 0 0 0 0 0 0 0 0 0

Octachlorostyrene 29082-74-4 0 0 0 0 0 0 0 0 0 0

Chlordane, oxy- 27304-13-8 0.016 0.022 0 0 0 0 0 0 0 0

Heptachlor Epoxide 1024-57-3 0 0.008 0 0.006 0 0 0 0 0 0

Chlordane, gamma (trans) 5103-74-2 0 0 0 0 0 0 0 0 0 0

Chlordane, alpha (cis) 5103-71-9 0 0 0 0 0.016 0 0 0 0 0

Nonachlor, trans- 39765-80-5 0 0 0 0 0 0 0 0 0 0

Nonachlor, cis- 5103-73-1 0 0 0 0 0 0 0 0 0 0

alpha-Endosulphan 959-98-8 0 0 0 0 0 0 0.054 0.086 0 0.085

beta-Endosulphan 33213-65-9 0.169 0.215 0.119 0.115 0.146 0 0.041 0 0 0.016

Dieldrin 60-57-1 0.003 0.014 0.031 0.008 0.002 0.106 0.001 0.005 0.053 0.031

2,4'-DDD 53-19-0 0 0 0 0 0 0 0 0 0 0

4,4'-DDD 72-54-8 0 0 0 0 0.066 1.456 0.064 0.039 0.018 0

2,4'-DDE 3424-82-6 0 0 0 0 0 0 0 0 0 0

4,4'-DDE 72-55-9 0 0 0 0.001 0.644 3.189 1.426 0.508 0.561 0.105

2,4'-DDT 789-02-6 0 0 0 0 0 0 0 0 0 0

4,4'-DDT 50-29-3 0 0 0 0 0.081 1.159 0.331 0.175 0 0

Captan * 133-06-2 0 0 0 0 0 0 0 0 0 0

Perthane * 72-56-0 0 0 0 0 0 0 0 0 0 0

Endrin 72-20-8 0 0 0 0 0.001 0.246 0.016 0 0 0

Endosulphan Sulphate 1031-07-8 0.615 0 0 0.009 0.408 0.12 0.239 0.07 0 0.024

Mirex 2385-85-5 0.005 0 0.003 0.005 0.037 0.038 0.032 0.021 0.019 0

Methoxychlor 72-43-5 0 0 0 0 0 0 0 0 0 0

Endrin Ketone 53494-70-5 0 0 0 0 0 0.101 0 0 0 0

Desethylatrazine 6190-65-4 0 0 0 0 0 0 0 0 0 0

Simazine 122-34-9 0 0 0 0 0 0 0 0 0 0

Atrazine 1912-24-9 0 0 0 0 0 0 0 0 0 0

Ametryn * 834-12-8 0 0 0 0 0 0 0 0 0 0

Metribuzin * 21087-64-9 0 0 0 0 0 0 0 0 0 0

Cyanazine * 21725-46-2 0 0 0 0 0 0 0 0 0 0

Hexazinone * 51235-04-2 0 0 0 0 0 0 0 0 0 0

Methamidophos * 10265-92-6 0 0 0 0 0 0 0 0 0 0

Phorate * 298-02-2 0 0 0 0 0 0 0 0 0 0

Terbufos * 13071-79-9 0 0 0 0 0 0 0 0 0 0

Diazinon-Oxon 962-58-3 0 0 0 0 0 0 0 0 0 0

Diazinon 333-41-5 0.067 0 0 0.114 0 0 0 0 0 0

Disulfoton * 298-04-4 0 0 0 0 0 0 0 0 0 0

Fonofos 944-22-9 0 0 0 0 0 0 0 0 0 0

Dimethoate * 60-51-5 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Methyl * 5598-13-0 0 0 0 0 0 0 0 0 0 0

Parathion-Methyl * 298-00-0 0 0 0 0 0 0 0 0 0 0

Pirimiphos-Methyl * 29232-93-7 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos * 2921-88-2 0.145 0 0.035 0.096 0.126 0.018 0 0 0 0.071

Fenitrothion * 122-14-5 0 0 0 0 0 0 0 0 0 0

Malathion * 121-75-5 0 0 0 0 0 0 0 0 0 0

Parathion-Ethyl * 56-38-2 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Oxon * 5598-15-2 0 0 0 0 0 0 0 0 0 0

Disulfoton Sulfone * 2497-06-5 0 0 0 0 0 0 0 0 0 0

Ethion * 563-12-2 0 0 0 0 0 0 0 0 0 0

Phosmet * 732-11-6 0 0 0 0 0 0 0 0 0 0

Azinphos-Methyl 86-50-0 0 0 0 0 0 0 0 0 0 0

Permethrin 52645-53-1 0 0 0 0 0 0 0 0 0 0

Cypermethrin 52315-07-8 0 0 0 0 0 0 0 0 0 0

Page 59: Contaminacion HNTS 2013 Final Report_Spanish William Eldridge

58

Appendix Table 4 (Continued)

Watershed Ocean Rio Térraba Rio Sierpe Rio Sierpe Rio Sierpe Rio Térraba Rio Térraba Rio Térraba Rio Térraba Mangrove

Map# 1 6 15 20 21 10 10 10 10 2

Date 11/7/2011 8/21/2011 11/3/2011 8/19/2011 8/19/2011 8/20/2011 8/20/2011 8/20/2011 8/20/2011 8/21/2011

Name Robalo negro Sea catfish Tilapia Tilapia Tilapia Tilapia Tilapia Tilapia Tilapia Piangua

Species

Centropomus nigrescens Cathorops sp. Oreochromis niloticus Oreochromis niloticus

Oreochromis

niloticus

Oreochromis

niloticus

Oreochromis

niloticus

Oreochromis

niloticus

Oreochromis

niloticus

Anadara

tuberculosa

No. fish in sample 1 3 1 1 1 1 1 1 1 2

Tissue Skin-on fillet Whole fish (N=3), 15 grams Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Skin-on fillet Whole clam

TL (mm) 581 63-85 149 208 187 321 321 223 184 -

Wt (g) 1600.0 1.9-4.53 71.5 187.3 138.4 660.0 660.0 271.2 143.9 -

% Lipid 0.27 2.29 0.67 0.38 0.86 1.53 1.03 1.25 0.82 0.60

Tecnazene 117-18-0 0 0 0 0 0 0 0 0 0 0

Hexachlorobenzene 118-74-1 0.005 0.02 0.019 0.017 0 0.133 0.059 0.039 0.07 0.009

Quintozene 82-68-8 0 0 0 0 0 0 0 0.036 0 0

Heptachlor 76-44-8 0 0.002 0 0 0 0 0 0 0 0

HCH, alpha 319-84-6 0 0 0 0 0 0 0 0 0 0

HCH, gamma 58-89-9 0 0 0 0 0 0 0 0 0 0

HCH, beta 319-85-7 0 0 0 0 0 0 0 0.022 0 0

HCH, delta 319-86-8 0 0 0 0 0 0 0 0 0 0

Chlorothalonil * 1897-45-6 0 0 0 0 0 0 0 0 0 0

Aldrin 309-00-2 0.004 0 0 0 0 0.013 0 0.012 0 0

Dacthal * 1861-32-1 0 0 0 0 0 0 0 0 0 0

Octachlorostyrene 29082-74-4 0 0 0 0 0 0 0 0 0 0

Chlordane, oxy- 27304-13-8 0 0 0 0 0 0.054 0.054 0.038 0.022 0

Heptachlor Epoxide 1024-57-3 0 0 0 0 0 0.346 0.178 0.115 0.071 0

Chlordane, gamma (trans) 5103-74-2 0 0 0 0 0 0.063 0.035 0 0 0

Chlordane, alpha (cis) 5103-71-9 0 0 0 0 0 0.111 0.034 0.052 0 0

Nonachlor, trans- 39765-80-5 0 0 0 0 0 0.301 0.159 0.126 0.076 0

Nonachlor, cis- 5103-73-1 0 0 0 0 0 0.102 0.058 0.063 0.047 0

alpha-Endosulphan 959-98-8 0.023 0.211 0.015 0.063 0 0.081 0 0.056 0 0.083

beta-Endosulphan 33213-65-9 0.023 0.213 0.057 0 0 0.069 0.06 0.03 0.086 0.107

Dieldrin 60-57-1 0.025 0.078 0.025 0.137 0.281 1.601 0.906 0.677 0.515 0.001

2,4'-DDD 53-19-0 0 0 0 0 0 0.31 0.156 0.082 0.073 0

4,4'-DDD 72-54-8 0 0.017 0.146 0.12 0.082 21.964 12.664 8.794 6.464 0

2,4'-DDE 3424-82-6 0 0 0 0 0 0.1 0.034 0 0 0

4,4'-DDE 72-55-9 0.224 0.277 1.066 0.847 0.44 19.146 10.546 9.216 7.176 0

2,4'-DDT 789-02-6 0 0 0 0 0 0.121 0.029 0 0.012 0

4,4'-DDT 50-29-3 0 0.03 0 0 0 7.598 4.038 2.878 1.598 0

Captan * 133-06-2 0 0 0 0 0 0 0 0 0 0

Perthane * 72-56-0 0 0 0 0 0 0 0 0 0 0

Endrin 72-20-8 0 0.004 0 0 0 1.655 0.924 0.527 0.475 0.011

Endosulphan Sulphate 1031-07-8 0 3.162 0.046 0.051 0.036 0.081 0.085 0.13 0.052 0.328

Mirex 2385-85-5 0.024 0.163 0 0 0 0.019 0.014 0.016 0 0

Methoxychlor 72-43-5 0 0 0 0 0 0 0 0 0 0

Endrin Ketone 53494-70-5 0 0 0 0 0 0.357 0.382 0.052 0.169 0

Desethylatrazine 6190-65-4 0 0 0 0 0 0 0 0 0 0

Simazine 122-34-9 0 0 0 0 0 0 0 0 0 0

Atrazine 1912-24-9 0 5.718 0 0 0 0 0 0 0 0

Ametryn * 834-12-8 0 0.2 0 0 0.089 0 0 0 0 0

Metribuzin * 21087-64-9 0 0 0 0 0 0 0 0 0 0

Cyanazine * 21725-46-2 0 0 0 0 0 0 0 0 0 0

Hexazinone * 51235-04-2 0 0 0 0 0 0 0 0 0 0

Methamidophos * 10265-92-6 0 0 0 0 0 0 0 0 0 0

Phorate * 298-02-2 0 0 0 0 0 0 0 0 0 0

Terbufos * 13071-79-9 0 0 0 0 0 0 0 0 0 0

Diazinon-Oxon 962-58-3 0 0 0 0 0 0 0 0 0 0

Diazinon 333-41-5 0 0.724 5.237 0 0 0 0 0 0 0

Disulfoton * 298-04-4 0 0 0 0 0 0 0 0 0 0

Fonofos 944-22-9 0 0 0 0 0 0 0 0 0 0

Dimethoate * 60-51-5 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Methyl * 5598-13-0 0 0 0 0 0 0 0 0 0 0

Parathion-Methyl * 298-00-0 0 0 0 0 0 0 0 0 0 0

Pirimiphos-Methyl * 29232-93-7 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos * 2921-88-2 0.074 3.53 0 0 0 0.055 0.121 0 0.027 0

Fenitrothion * 122-14-5 0 0 0 0 0 0 0 0 0 0

Malathion * 121-75-5 0 0 0 0 0 0 0 0 0 0

Parathion-Ethyl * 56-38-2 0 0 0 0 0 0 0 0 0 0

Chlorpyriphos-Oxon * 5598-15-2 0 0 0 0 0 0 0 0 0 0

Disulfoton Sulfone * 2497-06-5 0 0 0 0 0 0 0 0 0 0

Ethion * 563-12-2 0 0 0 0 0 0 0 0 0 0

Phosmet * 732-11-6 0 0 0 0 0 0 0 0 0 0

Azinphos-Methyl 86-50-0 0 0 0 0 0 0 0 0 0 0

Permethrin 52645-53-1 0 2.118 0 0 0 0 0 0 0 0

Cypermethrin 52315-07-8 0 0.154 0 0 0 0.113 0.305 1.066 0 0

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Appendix Table 4 (Continued)

Watershed Mangalar Mangrove Mangrove Mangalar Rio Sierpe Rio Sierpe

Map# 2 3 4 4 12 22

Date 11/5/2011 8/17/2011 8/16/2011 11/5/2011 8/22/2011 8/21/2011

Name Piangua Piangua Piangua Piangua Shrimp Shrimp

Species Anadara tuberculosa Anadara tuberculosa Anadara tuberculosa Anadara tuberculosa Shrimp Shrimp

No. fish in sample 6 3 3 4 15 13

Tissue Whole clam Whole clam Whole clam Whole clam Whole shrimp Whole shrimp

TL (mm) - - - - - -

Wt (g) - - - - - -

% Lipid 0.36 0.52 0.56 0.54 3.54 2.45

Tecnazene 117-18-0 0 0 0 0 0 0

Hexachlorobenzene 118-74-1 0 0.011 0.003 0 0.024 0.007

Quintozene 82-68-8 0 0 0 0 0 0

Heptachlor 76-44-8 0 0.006 0.002 0 0 0

HCH, alpha 319-84-6 0 0 0 0 0 0

HCH, gamma 58-89-9 0 0 0 0 0 0

HCH, beta 319-85-7 0 0 0 0 0 0

HCH, delta 319-86-8 0 0 0 0 0 0

Chlorothalonil * 1897-45-6 0 0 0 0 0 0

Aldrin 309-00-2 0 0.001 0 0 0 0

Dacthal * 1861-32-1 0 0 0 0 0 0

Octachlorostyrene 29082-74-4 0 0 0 0 0 0

Chlordane, oxy- 27304-13-8 0 0 0 0 0 0

Heptachlor Epoxide 1024-57-3 0 0 0 0 0 0

Chlordane, gamma (trans) 5103-74-2 0 0 0 0 0 0

Chlordane, alpha (cis) 5103-71-9 0 0 0 0 0 0

Nonachlor, trans- 39765-80-5 0 0 0 0 0 0

Nonachlor, cis- 5103-73-1 0 0 0 0 0 0

alpha-Endosulphan 959-98-8 0 0.069 0.027 0 0 0

beta-Endosulphan 33213-65-9 0 0 0.07 0 0 0

Dieldrin 60-57-1 0 0 0 0.013 0 0.152

2,4'-DDD 53-19-0 0 0 0 0 0 0

4,4'-DDD 72-54-8 0 0 0 0 0 0

2,4'-DDE 3424-82-6 0 0 0 0 0 0

4,4'-DDE 72-55-9 0 0 0 0 0.005 0.89

2,4'-DDT 789-02-6 0 0 0 0 0 0

4,4'-DDT 50-29-3 0 0 0 0 0 0

Captan * 133-06-2 0 0 0 0 0 0

Perthane * 72-56-0 0 0 0 0 0 0

Endrin 72-20-8 0 0 0 0 0 0

Endosulphan Sulphate 1031-07-8 0.049 0 0 0 0 0

Mirex 2385-85-5 0.001 0 0 0 0.005 0.016

Methoxychlor 72-43-5 0 0 0 0 0 0

Endrin Ketone 53494-70-5 0 0 0 0 0 0

Desethylatrazine 6190-65-4 0 0 0 0 0 0

Simazine 122-34-9 0 0 0 0 0 0

Atrazine 1912-24-9 0 0 0 0 0 0

Ametryn * 834-12-8 0 0 0 0 0 0

Metribuzin * 21087-64-9 0 0 0 0 0 0

Cyanazine * 21725-46-2 0 0 0 0 0 0

Hexazinone * 51235-04-2 0 0 0 0 0 0

Methamidophos * 10265-92-6 0 0 0 0 0 0

Phorate * 298-02-2 0 0 0 0 0 0

Terbufos * 13071-79-9 0 0 0 0 0 0

Diazinon-Oxon 962-58-3 0 0 0 0 0 0

Diazinon 333-41-5 0 0 0 0 0 0

Disulfoton * 298-04-4 0 0 0 0 0 0

Fonofos 944-22-9 0 0 0 0 0 0

Dimethoate * 60-51-5 0 0 0 0 0 0

Chlorpyriphos-Methyl * 5598-13-0 0 0 0 0 0 0

Parathion-Methyl * 298-00-0 0 0 0 0 0 0

Pirimiphos-Methyl * 29232-93-7 0 0 0 0 0 0

Chlorpyriphos * 2921-88-2 0 0 0 0 0 0

Fenitrothion * 122-14-5 0 0 0 0 0 0

Malathion * 121-75-5 0 0 0 0 0 0

Parathion-Ethyl * 56-38-2 0 0 0 0 0 0

Chlorpyriphos-Oxon * 5598-15-2 0 0 0 0 0 0

Disulfoton Sulfone * 2497-06-5 0 0 0 0 0 0

Ethion * 563-12-2 0 0 0 0 0 0

Phosmet * 732-11-6 0 0 0 0 0 0

Azinphos-Methyl 86-50-0 0 0 0 0 0 0

Permethrin 52645-53-1 0 0 0 0 0 0

Cypermethrin 52315-07-8 0 0 0 0 0 0

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Appendix Table 5: Consumption recommendations to avoid non-carcinogenic health effects of pesticides. Values are the recommended maximum

number of 227 g (0.5 lb) meals per month of contaminanted fish or shellfish for a 70 kg (154 lbs) person. Analysis was limited to chemicals that were

above detection limits. Species Machaca

Pargo colorado

Robalo

robalo

Robalo

chucumite

Robalo

robalo

Robalo

chucumite

Robalo

negro

Robalo

chucumite

Waterbody Rio Sierpe Rio Térraba Ocean Rio Sierpe Market Rio Sierpe Mangrove Rio Térraba

Map # 14 18 19 24 6 10 1 17 22 M M 13 23 24 2 7 6 10

Season Nov. Nov. Nov. Nov. Nov. Aug. Nov. Aug. Aug. Aug. Aug. Aug. Nov. Nov. Aug. Aug. Nov. Aug.

Number 1 1 1 1 2 1 3 1 1 1 1 1 1 2 3 2 1 1

% Lipid - - - - - - - 0.67 0.76 0.69 0.47 0.45 1.76 1.04 0.63 0.59 0.74 0.88

Captan

9125052

Chlordane

Chlordane, oxy- 670485

1564464 293337 7040088

426672

880011 426672 Chlordane, gamma (trans) 41905

1173348 36383

Chlordane, alpha (cis) 213336

117335

293337

Nonachlor, trans- 114473

670485 Nonachlor, cis- 134097

938678 1877357

938678

156446

Chlorothalonil 8282457 2607440

11733480 40229075 20114537 84481057

140801762 4,4'-DDT 4106 126848 38158 213336 347659 9598

11122 426672 2346696

57943

2,4'-DDD 19079 938678 361030 180515

48385

426672 4,4'-DDD 2314 39112 36667 48890 228946 7982

670485 8336 126848 670485

71112

2,4'-DDE 99859

4693392 4,4'-DDE 758 4864 7783 17192 45789 4765 220003

27772 109149 142224 806 10667 18588 391116

4693392 7288

2,4'-DDT 59410

195558 Dieldrin 61 6258 1376 6902 17067 91 9916 27608 67048

16762 646 26074 36103 117335 20860 58667 234670

Aldrin

70401

10831

281604 422405 187736

28160

Endosulfan

alpha-Endosulphan 242762 640008 284448 405185 428294 79549 492601 828246 306091

2085952 1444121

7040088 beta-Endosulphan 6257856 1522181 288824

674499 6006 1362598 2964248

866472 1309784 5120064

329361 337250 489745 385758

Endosulphan sulphate 557631 1816797 741062

1072775 96110 982338 1444121

166629

2681938 37547137 101723

6257856 138041

Endrin 10315

187736 201145 469339 176002 367309

201145

68684 2816035

8448106

2816035

Endrin ketone 165649 HCH, beta

Heptachlor 260744

1877357 75700

4693392

2346696

14080176 Heptachlor Epoxide 1151 6779

17433 8716 2302

8135

10169

30507 30507 20338

Hexachlorobenzene 183157 192549 300377 250314 341338 192549 2048026 1877357 1501885 1877357 3754714 1251571 357592 3003771 3218326 5006285 1877357 1501885

Mirex 15263 60560 67048 208595 139063 64736 312893 625786 50739 234670 1877357 14441 56890 68268 804581 1251571 375471 50739

Octachlorostyrene 1340969163 Quintozene

Ametryn

Atrazine

Chlorpyriphos

165649 34342 31641 3798 8092 19027 78223 40812

16404 160916 29334 22349

Diazinon

31590

19018

152808

57638

Pirimiphos-Methyl 319278

Terbufos 1805

Cypermethrin

12420

Permethrin

8855457

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Appendix Table 5 (Continued).

Species Robalo negro Sea catfish Tilapia Piangua Shrimp

Waterbody Rio Térraba Ocean Rio Térraba Rio Sierpe Rio

Térraba

Mangrove Rio Sierpe

Map # 10 1 6 15 20 21 10 2 3 4 12 22

Season Aug. Nov. Aug. Nov. Aug. Aug. Aug. Aug. Nov. Aug. Aug. Nov. Aug. Aug.

Number 3 3 1 1 1 1 3 1 1 1 1 1 1 1

% Lipid 0.69 0.83 2.29 0.67 0.38 0.86 1.2 0.6 0.36 0.52 0.56 0.54 3.54 2.45

Captan

Chlordane

Chlordane, oxy-

111747

Chlordane, gamma (trans)

191567

Chlordane, alpha (cis)

95297

Nonachlor, trans-

28359

Nonachlor, cis-

69532

Chlorothalonil

4,4'-DDT 8457 156446

1165

2,4'-DDD

30231

4,4'-DDD 9032 782232 276082 32147 39112 57236 376

2,4'-DDE

140101

4,4'-DDE 2748 15820 16944 4403 5541 10667 407

938678 5273

2,4'-DDT

115886

Dieldrin 12572 12918 6017 18774 3426 1670 508 469339

36103

3088

Aldrin 211203

45057

281604

Endosulfan

alpha-Endosulphan 1206872 1564464 266923 3754714 893979

1644400 678563

816242 2085952

beta-Endosulphan 4121027 4332362 264416 988083

919522 526362

804581

Endosulphan sulphate 393851 7040088 17812 1224363 1104328 1564464 647364 171709 1149402

Endrin 32245 704009

3146 256003

Endrin ketone 83645

11733

HCH, beta

1706688026

Heptachlor 2346696 2346696

782232 2346696

Heptachlor epoxide

687

Hexachlorobenzene 2252828 1877357 375471 395233 441731

99793 834381

682675 2503142

312893 1072775

Mirex 61891 130978 11518

153254

1877357

375471 117335

Octachlorostyrene

Quintozene

3128928

Ametryn 422405

949225 Atrazine 57457

Chlorpyriphos 469339 58263 798

55488

Diazinon 9076 1255

Pirimiphos-Methyl

Terbufos

Cypermethrin 609531

253013

Permethrin 221595

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Appendix Table 6: Consumption recommendations to avoid carcinogenic health effects of pesticides. Values are the recommended maximum

number of 227 g (0.5 lb) meals per month of contaminanted fish or shellfish for a 70 kg (154 lbs) person. Analysis was limited to chemicals that were

above detection limits.

Species Machaca Pargo

colorado

Robalo

robalo

Robalo

chucumite

Robalo

robalo

Robalo

chucumite

Robalo

negro

Robalo

chucumite

Robalo

negro

Waterbody Rio Sierpe Rio Térraba Ocean Rio Sierpe Market Rio Sierpe Mangrove Rio Térraba Ocean

Site # 14 18 19 24 6 10 1 17 22 M M 13 23 24 2 7 6 10 10 1

Season Nov. Nov. Nov. Nov. Nov. Aug. Nov. Aug. Aug. Aug. Aug. Aug. Nov. Nov. Aug. Aug. Nov. Aug. Aug. Nov.

Number 1 1 1 1 2 1 3 1 1 1 1 1 1 2 3 2 1 1 3 3

% Lipid - - - - - - - 0.67 0.76 0.69 0.47 0.45 1.76 1.04 0.63 0.59 0.74 0.88 0.69 0.83

Chlordane

Chlordane, oxy- 38313

89398 16762 402291

24381

50286 24381

Chlordane, gamma

(trans) 2395

67048 2079

Chlordane, alpha (cis) 12191

6705

16762

Nonachlor, trans- 6541

38313

Nonachlor, cis- 7663

53639 107278

53639

8940

4,4'-DDT 242 7462 2245 12549 20451 565

654 25098 138041

3408 497

2,4'-DDD 1122 55216 21237 10619

2846

25098

4,4'-DDD 136 2301 2157 2876 13467 470

39440 490 7462 39440

4183 531 46014

2,4'-DDE 5874

276082

4,4'-DDE 45 286 458 1011 2693 280 12941

1634 6421 8366 47 627 1093 23007

276082 429 162 931

2,4'-DDT 3495

11503

Dieldrin 0.8 78 17 86 213 1.1 124 345 838

210 8 326 451 1467 261 733 2933 157 161

Aldrin

1467

226

5867 8800 3911

587

4400

Heptachlor 4011

28882 1165

72206

36103

216618

36103

Heptachlor epoxide 97 573

1474 737 195

688

860

2579 2579 1719

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Appendix Table 6 (Continued)

Species Sea catfish Tilapia Piangua Shrimp

Waterbody Rio Térraba Rio Sierpe Rio Térraba Mangrove Rio Sierpe

Site # 6 15 20 21 10 2 3 4 12 22

Season Aug. Nov. Aug. Aug. Aug. Aug. Nov. Aug. Aug. Nov. Aug. Aug.

Number 1 1 1 1 3 1 1 1 1 1 1 1

% Lipid 2.29 0.67 0.38 0.86 1.2 0.6 0.36 0.52 0.56 0.54 3.54 2.45

Chlordane

Chlordane, oxy- 6386

Chlordane, gamma (trans) 10947

Chlordane, alpha (cis) 5446

Nonachlor, trans- 1621

Nonachlor, cis- 3973

4,4'-DDT 9203 69

2,4'-DDD 1778

4,4'-DDD 16240 1891 2301 3367 22

2,4'-DDE 8241

4,4'-DDE 997 259 326 627 24 55216 310

2,4'-DDT 6817

Dieldrin 75 235 43 21 6 5867 451 39

Aldrin 939 5867

Heptachlor 36103 12034 36103

Heptachlor epoxide 58

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Appendix Figure 1: Sample sites and gear used to sample fish and shellfish

Site 1 (8.87721, -83.65120) Ocean

Gear – Gill net (fish collected by family of Marcelo Angelos)

Site 2 (8.95252, -83.61710) Isla Boca Brava

Gear – Piangua by hand, fish by cast net

Site 3 (8.93108, -83.61389) Isla Boca Chica

Gear – Piangua by hand

Site 4 (8.88943 -83.60350) Isla Zacate

Gear – Piangua by hand

Site 5 (8.85064, -83.59220) Boca Guarumal

Gear – Beach seine, hook and line

Site 6 (8.98812, -83.59155) Estero Tagual, Estero Rey

Gear – Gill net

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Site 7 (8.90578, -83.57911389) Estero Camibar

Gear – Hook and line

Site 8 (8.96253, -83.55042) Rice canal, Rio Terraba

Gear – Cast net

Site 9 (8.86305, -83.53841) Estero Guarumal

Gear – Hook and line

Site 10 (8.95388, -83.52421) Rio Belsar Puerto Cortez

Gear – Cast net, hook and line

Site 11 (8.85630, -83.49246) Rio Sierpe

Gear – Hook and line

Site 12 (8.84253, -83.47831) Toma agua

Gear – Dip net, cast net

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Site 13 (8.87863, -83.46943) Estero Azul

Gear – Hook and line

Site 14 (8.89475, -83.46643) Estero Azul

Gear – Hook and line

Site 15 (8.88128, -83.46402) Eleotrid

Gear – Cast net

Site 16 (8.89669, -83.46178) Finca Julia

Gear – Cast net

Site 17 (8.85247, -83.45369)Rio Tigre

Gear – Hook and line

Site 18 (8.85792, -83.44739) Estero Negro

Gear – Gill net

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Site 19 (8.82039, -83.44031) Rio Chacuaco

Gear – Gill net

Site 20 (8.90364, -83.44158) Rice canal

Gear – Cast net

Site 21 (8.90414, -83.43083) Rice channel

Gear – Cast net, Seine

Site 22 (8.84683, -83.40781) Estero Olla

Gear – Hook and line, Shrimp seine

Site 23 (8.80410, -83.39712) Rio Tabago

Gear – Gill net

Site 24 (8.83542, -83.3743) Patagallena

Gear – Gill net

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Appendix Figure 2. Overnight 18-19 Aug. 2011 temperature and dissolved oxygen recorded at 2 minute

intervals in the Rio Sierpe headwaters (N8.80415, W83.32253). A rain storm passed over the site between

approximately 13:00 and 18:00 hours.

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Appendix Figure 3. Overnight 21-22 Aug. 2011 temperature, dissolved oxygen and specific conductivity

recorded at 15 minute intervals in the Rio Sierpe at the village of Sierpe (N8.857511, W83.472607). A small

blip in specific conductance between 22:26 and 1:11 hours corresponds with the daily high tide.

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Appendix Figure 4. Water physiochemistry in the mainstem Rio Sierpe at a depth of 0.5m (solid line and empty

symbols) and 4m (dashed line and filled symbols). Measurements taken 13:15-14:47 17 Aug 2011 (5-9 river

kilometers upstream from the ocean at Boca Zacate) and 8:15-10:04 18 Aug 2011 (9-23 river kilometers

upstream from the ocean at Boca Guarumal).

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Appendix Figure 5. Average daily temperature at tidally influenced locations of transplanted piangua on Isla

Zacate (N8.85064, W83.59220) and Isla Boca Brava (N8.95252, W83.61710).


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