Air monitoring of new and legacy POPs in the Group of Latin America and Caribbean (GRULAC) region.

A special initiative in the Global Atmospheric Passive Sampling (GAPS) Network was implemented to provide information on new and emerging persistent organic pollutants (POPs) in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale atmospheric concentrations of the new and emerging POPs hexachlorobutadiene (HCBD), pentachloroanisole (PCA) and dicofol indicators (breakdown products) are reported for the first time. HCBD was detected in similar concentrations at all location types (<20-120 pg/m3). PCA had elevated concentrations at the urban site Concepción (Chile) of 49-222 pg/m3, with concentrations ranging <1-8.5 pg/m3 at the other sites in this study. Dicofol indicators were detected at the agricultural site of Sonora (Mexico) at concentrations ranging 30-117 pg/m3. Legacy POPs, including a range of organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were also monitored to compare regional atmospheric concentrations over a decade of monitoring under the GAPS Network. γ-hexachlorocyclohexane (HCH) and the endosulfans significantly decreased (p < 0.05) from 2005 to 2015, suggesting regional levels are decreasing. However, there were no significant changes for the other legacy POPs monitored, likely a reflection of the persistency and slow decline of environmental levels of these POPs. For the more volatile OCs, atmospheric concentrations derived from polyurethane foam (PUF) (acting as an equilibrium sampler) and sorbent impregnated PUF (SIP) (acting as a linear phase sampler), were compared. The complimentary methods show a good agreement of within a factor of 2-3, and areas for future studies to improve this agreement are further discussed.

Atmospheric Concentrations of New Persistent Organic Pollutants and Emerging Chemicals of Concern in the Group of Latin America and Caribbean (GRULAC) Region.

A special initiative was run by the Global Atmospheric Passive Sampling (GAPS) Network to provide atmospheric data on a range of emerging chemicals of concern and candidate and new persistent organic pollutants in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale data for a range of flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and a range of alternative FRs (novel FRs) are reported over 2 years of sampling with low detection frequencies of the novel FRs. Atmospheric concentrations of the OPEs were an order of magnitude higher than all other FRs, with similar profiles at all sites. Regional-scale background concentrations of the poly- and perfluoroalkyl substances (PFAS), including the neutral PFAS (n-PFAS) and perfluoroalkyl acids (PFAAs), and the volatile methyl siloxanes (VMS) are also reported. Ethyl perfluorooctane sulfonamide (EtFOSA) was detected at highly elevated concentrations in Brazil and Colombia, in line with the use of the pesticide sulfluramid in this region. Similar concentrations of the perfluoroalkyl sulfonates (PFAS) were detected throughout the GRULAC region regardless of location type, and the VMS concentrations in air increased with the population density of sampling locations. This is the first report of atmospheric concentrations of the PFAAs and VMS from this region.

Towards a regional passive air sampling network and strategy for new POPs in the GRULAC region: Perspectives from the GAPS Network and first results for organophosphorus flame retardants.

A discussion is presented on the limitations for air monitoring studies around the Group of Latin American and Caribbean Countries (GRULAC), highlighting key issues requiring further attention, and reports on how a special initiative is addressing these limitations. Preliminary results are presented for the first reported data on organophosphorus flame retardant (OPFR) concentrations in outdoor air from the GRULAC region. At the majority of sites the concentrations and the profile of the OPFRs detected were similar with tris (chloroisopropyl) phosphate (TCPP) dominating (

Assessing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in air across Latin American countries using polyurethane foam disk passive air samplers.

A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.

Pesticide sequestration in passive samplers (SPMDs): considerations for deployment time, biofouling, and stream flow in a tropical watershed.

Semi-permeable membrane devices (SPMDs) provide an informative and cost-effective approach for monitoring contaminants in remote tropical streams. Estimation and interpretation of contaminant concentrations in streams derived from SPMDs can vary based on a number of environmental factors, including stream flow, biofouling, and deployment time. In three one-month long trials, SPMDs were concurrently deployed for 4, 15, and 28 days at three stream sites in an extensive agricultural area of southeastern Costa Rica. Water, bottom sediment, and suspended solids grab samples were also collected and several environmental variables were monitored at corresponding time intervals during each month-long study period. At all three sites, SPMD concentrations of the widely used insecticide chlorpyrifos increased with deployment time, with no relationship between SPMD biofouling and pesticide sequestration. Differences in SPMD chlorpyrifos sequestration among sites are likely due to differences in stream chlorpyrifos concentration rather than differences in SPMD sampling rates. The longer exposure period of SPMDs allowed for the detection of lower concentrations of chlorpyrifos, terbufos, and difenoconazole compared to water grab samples. In addition to the use of appropriate performance reference compounds (PRCs), other environmental variables such as stream turbidity, flow regime, stream morphology, and knowledge of pesticide application methods are important considerations for optimizing SPMD deployment and data interpretation in tropical regions.

Water quality and macroinvertebrate community response following pesticide applications in a banana plantation, Limon, Costa Rica.

Pesticides used in banana production may enter watercourses and pose ecological risks for aquatic ecosystems. The occurrence and effects of pesticides in a stream draining a banana plantation was evaluated using chemical characterization, toxicity testing and macrobenthic community composition. All nematicides studied were detected in the surface waters of the banana plantation during application periods, with peak concentrations following applications. Toxicity tests were limited to the carbofuran application and no toxicity was observed with the acute tests used. However, since pesticide concentrations were generally below the lowest LC50 value for crustaceans but above calculated aquatic quality criteria, there remains a risk of chronic toxicity. Accurate ecological assessments of pesticide use in banana plantations are currently limited by the lack of local short-term chronic toxicity tests and tests using sensitive native species. Relatively constant levels of four pesticides (imazalil, thiabendazole, chlorpyrifos and propiconazole), which had toxic effects according to the 96h hydra and 21d daphnia chronic test, were recorded in the effluent of the packing plant throughout the study, indicating that the solid waste trap used in this facility was not effective in eliminating toxic chemicals. Certain taxa, such as Heterelmis sp. (Elmidae), Heteragrion sp. (Megapodagrionidae, Odonata), Caenis sp. (Caenidae, Ephemerotera), and Smicridea sp. (Hidropsychidae, Trichoptera), were more abundant at reference sites than in the banana farm waters, and may be good candidates for toxicity testing. Multivariate analyses of the macroinvertebrate communities clearly showed that the banana plantation sites were significantly different from the reference sites. Moreover, following the pesticide applications, all the banana plantation sites showed significant changes in community composition, with the same genera being affected at all sites and for all pesticides (terbufos, cadusafos and carbofuran). Consequently, the results presented here show that multivariate analysis of community composition was more sensitive in distinguishing pesticide effects than the toxicity tests and richness and composition measures used. We conclude that monitoring macroinvertebrate communities can be a powerful tool in the assessment of ecological effects of banana production.