Chromoproduct approach to achieve environmentally sound management of e-waste plastics: Colombian project case.

Research to prevent releases of brominated flame retardants listed as persistent organic pollutants by the Stockholm Convention (POP-BFRs) was conducted through an international cooperation project in Colombia. Six waste electrical and electronic equipment (WEEE) management facilities implemented: 1) sorting e-waste by product type and color (black, white, and other; henceforth called chromoproducts), 2) sampling test products and their plastic fraction (called sets, separated by polymer type), 3) monitoring mass, bromine and antimony contents by hand-held X-ray fluorescence (XRF) and POP-BFRs such as polybrominated diphenyl ethers (PBDEs) by gas chromatography and mass spectrometry (GC-MS), and 4) differentiated treatment according to categories that used the Restriction of Hazardous Substances in Electrical and Electronic Equipment Directive (RoHS) hazardousness threshold of 1000 mg ∑PBDEs/kg. This scheme led to the proposal of a methodology for WEEE management called the "chromoproduct approach". 994,230 products were managed and grouped into 222 chromoproducts, from which 77 were analyzed: 50 below RoHS hazardousness (BRH), 16 above RoHS hazardousness (ARH), and 11 unknown RoHS hazardousness (URH). XRF indicators using bromine and antimony contents could rule out pollution in BRH chromoproducts; however, categorization still required GC-MS. One ARH plastics sample had 3620 mg ∑PBDEs/kg, while no POP-BFRs were found in the BRH plastics sample. The implementation of the chromoproduct approach traced 153.6 tonnes of ARH plastics. BRH plastics composition was estimated and used in a pilot-scale closed-loop economic activity. The chromoproduct approach seems promising for avoiding POP-BFR releases and promoting the upcycling of recyclable e-waste plastics.

Persistent organic pollutants and polycyclic aromatic hydrocarbons in livers of stranded Arctocephalus australis in southern Brazilian beaches.

23 livers of South American fur seal (Arctocephalus australis) found stranded in southern Brazilian beaches were evaluated for Persistent Organic Pollutants (POPs) and Polycyclic Aromatic Hydrocarbons (PAHs). POPs (DDTs, mirex, eldrin, dieldrin, aldrin, isodrin, HCHs, chlordanes and PCBs) and PAHs in livers were Soxhlet extracted, analyzed and quantified using Gas Chromatography Tandem Mass Spectrometry (GC-TQMS). The main POPs found were PCBs and DDTs, totaling 81 %. Among pesticides, mirex followed DDTs, possibly due to usage in Uruguay, followed by Σdrins, ΣCHLs and ΣHCHs. Naphthalene was the major PAH found, while heavier compounds did not significantly bioaccumulate. Concentrations of POPs resembled previous findings for A. australis. Considering only juveniles, no POPs showed significant differences between sexes. Lipidic content, weight and length did not show any correlation with POP concentration. This was the first record of PAHs and PBDEs in South American fur seals, and the levels of these pollutants were relatively low.

Brominated flame retardants and natural organobrominated compounds in a vulnerable delphinid species along the Brazilian coast.

Guiana dolphins, Sotalia guianensis, are vulnerable to extinction along their distribution on the Brazilian coast and assessing chemical pollution is of utmost importance for their conservation. For this study, 51 carcasses of Guiana dolphins were sampled across the Brazilian coast to investigate legacy and emerging brominated flame retardants (BFRs) as well as the naturally-produced MeO-BDEs. PBDEs and MeO-BDEs were detected in all samples analyzed, whereas emerging BFRs were detected in 16 % of the samples, all in Rio de Janeiro state. PBDE concentrations varied between 2.24 and 799 ng.g-1 lipid weight (lw), emerging BFRs between 0.12 and 1.51 ng.g-1 lw and MeO-BDEs between 3.82 and 10,247 ng.g-1 lw. Concentrations of legacy and emerging BFRs and natural compounds varied considerably according to the sampling site and reflected both the local anthropogenic impact of the region and the diversity/mass of biosynthesizers. The PBDE concentrations are lower than what was found for delphinids in the Northern Hemisphere around the same sampling period and most sampling sites presented mean concentrations lower than the limits for endocrine disruption known to date for marine mammals of 460 ng.g-1 lw, except for sampled from Santa Catarina state, in Southern Brazil. Conversely, MeO-BDE concentrations are higher than those of the Northern Hemisphere, particularly close to the Abrolhos Bans and Royal Charlotte formation, that are hotspots for biodiversity. Despite the elevated concentrations reported for this group, there is not much information regarding the effects of such elevated concentrations for these marine mammals. The distinct patterns observed along the Brazilian coast show that organobrominated compounds can be used to identify the ecological segregation of delphinids and that conservation actions should be planned considering the local threats.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) in human breast milk from Colombia: A probabilistic risk assessment approach.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) are ubiquitous environmental contaminants. They were produced in relatively large volumes in the last century and are now subject to long-term monitoring and regulated under the United Nations Stockholm Convention (SC) on persistent organic pollutants (POPs). Though restricted, human exposure is still a concern and in some regions of the globe the information on the health risk is limited. Sixty breast milk samples from nursing mothers were collected between 2014 and 2015, residing in Bogota, Cartagena, and Medellin, which are industrialized cities in Colombia. This is the first comprehensive study to determine the concentrations in breast milk of PBDEs (n = 7), PCBs (n = 29), and OCPs (n = 28) in Colombia. The detection frequency of POPs, including BDE-47, CB-138, CB-153, CB-156, and CB-180, as well as several OCPs such as chloroneb, aldrins, HCHs, DDTs, and heptachlor, was found to be 100% in all samples tested. The mean concentrations of the analyzed legacy POPs were ∑3DDTs (423 ng/g lw) > chloroneb (50.1 ng/g lw) > ∑2permetrins (17.5 ng/g lw) > ∑2aldrins (16.7 ng/g lw) > 29 PCBs (15.04 ng/g lw) > ∑2chlordanes (CHLs) (11.2 ng/g lw) ≈ ∑3endosulfans (11.1 ng/g lw) > ∑2heptachlors (2.43 ng/g lw) > 7PBDEs (2.1 ng/g lw) > ∑4HCHs (0.58 ng/g lw). The results of this study suggest that the concentrations of DDTs were present in breast milk samples from Colombia at levels comparable to those found in previous studies conducted in other countries such as Brazil, Uruguay, Chile, and various Asian countries. The concentrations of PBDE and PCB congeners, as well as many pesticides, were found to be significantly correlated with each other. This suggests that these substances may have similar sources of exposure. The strength of the pair correlation among concentrations of POPs was assessed using Spearman's correlation coefficients, which varied from r = 0.62 for the association between BDE-47 and CB-153, to a high correlation of 0.99 for the correlation between γ-Chlordane and heptachlor. This suggests that these POPs may share similar sources, such as diet. An exposure assessment model obtained by Monte Carlo simulation showed that infants were exposed to low concentrations of POPs with exception of p,p'-DDE and Aldrin, in which 25th, 50th and 95th percentiles were greater than the threshold reference values of non-carcinogenic effects suggested by US-EPA regulations while the 90th percentile of pg TEQ/Kg-bw/day for dl-PCBs was above of the tolerable daily intake (TDI) proposed by the World Health Organization (WHO). Therefore, the health risk of infants exposed to OCPs and dl-PCBs should be exanimated continually through biomonitoring programs in the Colombian population.

Dynamic passive sampling of hydrophobic organic compounds in surface seawater along the South Atlantic Ocean east-to-west transect and across the Black Sea.

Mapping of hydrophobic organic compounds (HOCs) in surface seawater on an east-to-west transect of the South Atlantic Ocean (SAO) and across the Black Sea (BS) in 2016 was performed by a dynamic passive sampling device containing silicone-based passive samplers. In SAO as well as in BS the measurements confirmed freely dissolved concentrations of polychlorinated biphenyls, DDT and its metabolites, chlorobenzenes, cyclodiene pesticides, and brominated flame retardants in the range of units to low hundreds of pg per litre. The findings indicate that the spatial distribution of HOCs and emerging pollutants in the SAO and the BS is influenced by riverine inputs, ocean currents and atmospheric deposition from continental plumes. Observed concentration gradients indicate that eastern SAO receives DDT from sources in South Africa, whereas the emissions of endosulfan originate in South America. Elevated HOC concentrations in the northwestern BS are related to their discharge by rivers from the European continent.

First assessment of persistent organic pollutants in the Greater rhea (Rhea americana), a near-threatened flightless herbivorous bird of the Pampas grasslands.

Persistent organic pollutants (POPs) are still globally distributed and can exert different effects on ecosystems. Little is known about the occurrence of these contaminants in terrestrial birds from South America. In this study, POPs were assessed for the first time in a flightless herbivorous species from the Pampas grasslands, the Greater rhea (Rhea americana). Concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs) were determined in 18 samples of feathers from free-ranging and captive individuals inhabiting four sites with different land uses in central Argentina. Among the 16 POPs tested in those feathers, 6 PCBs (28, 52, 101, 138, 153, and 180) and 8 OCPs (α-HCH, ß-HCH, γ-HCH, p,p'-DDE, p,p'-DDD, o,p'-DDT, p,p'-DDT, and HCB) were quantified. No PBDEs were detected. The total concentration of POPs was higher in populations living in an intensive crop production area (agriculture 159 ng g -1 and farm: 97.53 ng g-1) compared with the population in an urban area (zoo 45.86 ng g-1) and an agroecosystem with extensive rearing of livestock (cattle rearing 36.77 ng g-1). PCBs were the most abundant pollutants in all the populations studied. Lower chlorinated CB 52 and CB 101 were the principal PCB congeners detected, representing at least 70% of the total quantified. All populations studied showed a DDE + DDD/DDT ratio > 1, indicating a historical application of this insecticide. This study provides a new contribution to the scarce data on POP concentrations in South American bird species. Further investigations are needed to evaluate their potential effects on the health of individuals and populations.

Preliminary assessment of exposure to persistent organic pollutants among pregnant women in Puerto Rico.

BACKGROUND: Puerto Rico has over 200 hazardous waste sites, as well as higher rates of several adverse health outcomes compared to the mainland US. In response to concerns of potential links between environmental contaminant exposure and preterm birth, the Puerto Rico Testsite for Exploring Contamination Threats (PROTECT) birth cohort was formed. Biomarkers of exposure for several contaminants have been found to be elevated in this cohort compared to women of child-bearing age in the National Health and Nutrition Examination Survey (NHANES). However, exposure to persistent organic pollutants (POPs) has not been evaluated. METHODS: In this preliminary analysis, we measured four classes of POPs, including perfluoroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and several persistent pesticides in serum samples collected at 16-20 weeks gestation from the first 48 women enrolled in PROTECT. We performed descriptive analyses for each analyte, assessed correlations between analytes using Spearman correlations, and compared serum levels in PROTECT women to levels in NHANES women aged 18-40. RESULTS: Several PFASs were detected in 96-100% of samples, with moderate to strong correlations between most PFASs (range r = 0.44-0.88). BDE47, BDE153, PCB 138-158, PCB153 and p,p'-dichlorodiphenyldichloroethene (p,p'-DDE) were detected in the majority of samples, with strong correlations between PCBs and p,p'-DDE (range r = 0.59-0.74). The median concentration for each analyte was lower than, sometimes by a factor of 4 (e.g. BDE47, p,p'-DDE), the median concentration reported in NHANES women aged 18-40. CONCLUSION: Although participants in the ongoing PROTECT birth cohort have higher exposure to many environmental contaminants, this preliminary study suggests that they have lower exposure to several POPS, specifically PCBs, OCPs, PFASs, and PBDEs.

Occurrence of flame retardants in landfills: A case study in Brazil.

Huge amounts of waste containing flame retardants reach landfills annually, which can result in environmental contamination if this type of solid residues is not properly managed. This study presents data concerning the occurrence of organophosphorus flame retardants (OPFRs), polybrominated diphenyl ethers (PBDEs) and new brominated flame retardants (NBFRs) in soil, dust, leachate and well water samples from a landfill in Brazil. Samples were collected in different points of the landfill site, including offices, concierge, electronic waste storage area, bulk waste storage area, a place where a recycling cooperative operates, leachate pound and wells. Most of the flame retardants (FRs) were quantified in soil samples (up to 2500 ng g-1). The tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were present at the highest levels in the site where bulk waste was disposed in the open air. The most abundant brominated FRs in soil samples were BDE-99, BDE-209, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and the highest levels were observed in the samples collected from the electronic waste storage area. Concerning dust samples, the highest levels of brominated FRs were observed in the electronic waste storage area, while the highest levels of OPFRs were observed in the landfill office. TCIPP, TDCIPP and tris(2-choroethyl) phosphate (TCEP) were quantified in the well water sample collected downstream the bulk waste area. Finally, six OPFRs were quantified in leachate at concentrations ranging from 14 to 965 ng L-1. In conclusion, this study demonstrates that an improper management of wastes containing FRs in landfills can potentially contaminate the surrounding environment and groundwater.

ASSESSMENT OF POLYCHLORINATED BIPHENYLS, ORGANOCHLORINE PESTICIDES, AND POLYBROMINATED DIPHENYL ETHERS IN THE BLOOD OF HUMBOLDT PENGUINS ( SPHENISCUS HUMBOLDTI) FROM THE PUNTA SAN JUAN MARINE PROTECTED AREA, PERU.

Persistent organic pollutants were assessed in Humboldt Penguins ( Spheniscus humboldti) from the Punta San Juan Marine Protected Area, Peru, in the austral winter of 2009. Plasma samples from 29 penguins were evaluated for 31 polychlorinated biphenyl (PCB) congeners and 11 organochlorine pesticides (OCPs) by using gas chromatography coupled to an ion trap mass spectrometer and for 15 polybrominated diphenyl ether (PBDE) congeners by using gas chromatography coupled with high-resolution mass spectrometry. The detection rate for PCBs in the samples was 69%, with congeners 105, 118, 180, and 153 most commonly detected. The maximum ΣPCB concentration was 25 ng/g. The detection rate for DDT, DDD, and/or DDE was higher than for other OCP residues (90%; maximum concentration=10 ng/g). The detection rate for PBDEs was 86%, but most concentrations were low (maximum ΣPBDE concentration=3.81 ng/g). This crucial breeding population of S. humboldti was not exposed to contaminants at levels detrimental to health and reproductive success; however, the identified concentrations of legacy and recently emerged toxicants underscore the need for temporal monitoring and diligence to protect this endangered species in the face of regional human population and industrial growth. These results also provide key reference values for spatial comparisons throughout the range of this species.

Determination of polybrominated diphenyl ethers in milk samples. Development of green extraction coupled techniques for sample preparation.

Ultrasound-assisted extraction (UAE), cloud point extraction (CPE), and ultrasound back-extraction (UABE) techniques have been coupled for lixiviation, preconcentration, and cleanup of polybrominated diphenyl ethers (PBDEs) from milk samples for determination by gas chromatography-electron capture detection (GC-ECD). Physicochemical parameters that affect the efficiency of the extraction system were investigated using a design of experiments based on multivariate statistical tools, and considering the sample matrix along the development. The coupling of the leaching step, UAE, enhanced ca. 3.5 times the extraction efficiency of the former sample preparation methodology (CPE-UABE) leading to cleaner sample extracts suitable for GC analysis. Under optimum conditions, the proposed methodology exhibits successful performance in terms of linearity and precision, with recoveries in the range of 68-70% and LODs within the range 0.05-0.5 ng/g dry weight (d.w.). The proposed sample preparation methodology coupled three green analytical techniques. It expands the application frontiers of CPE for the analysis of biological samples by GC. The optimized methodology was used for determination of PBDEs in powder milk samples, from both commercial and human sources.

Multimatrix measurement of persistent organic pollutants in Mar Chiquita, a continental saline shallow lake.

RAMSAR sites are determined by specific characteristics of the environment in terms of ecological productivity as well services for human development, but they are also one of the most threatened ecosystems. Thus, the objective of this work was to evaluate the dynamic of Persistent Organic Pollutants (POPs) in different biotic and abiotic matrixes of the RAMSAR site (wetlands with international importance), Mar Chiquita Lake. Sampling was performed according to land use (agricultural, urban, and industrial) at two stations: Laguna del Plata and Campo Mare. POPs were analyzed in superficial water (Sw), suspended particulate material (SPM), bottom sediment (Bs) and fish tissues (Odontesthes bonariensis). Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were analyzed by GC-ECD. HCHs, Endosulfans, DDTs, PCBs and PBDEs were found in all matrixes at both stations. The high persistence and transport processes are responsible for the occurrence of HCHs, DDTs and PCBs in Bs, SPM and fish tissues, even many years after their prohibition. PBDEs showed lower levels according to the scarcity of punctual sources in the area. Endosulfan showed variable amounts in agreement with application periods since this pesticide was used until a few years ago in this area. Finally, PCB levels overpassed the acceptable daily intake for human consumption being a risk for human health Thus, the present report confirms the occurrence of POPs in Mar Chiquita lake, alerting on the contribution of agricultural and urban pollutants in a RAMSAR site. Current results also raise concerns on biomagnification processes through the food web.

Occurrence and behavior of natural and anthropogenic (emerging and historical) halogenated compounds in marine biota from the Coast of Concepcion (Chile).

Fifty-five biota samples from the Coast of Concepcion (Chile) were analyzed for PBDEs, emerging brominated FRs, halogenated norbornenes and naturally-occurring MeO-PBDEs. PBDEs, MeO-PBDEs and halogenated norbornenes were detected at concentration levels ranging from 11 to 170, nd to 118 and nd to 5.8 ng/g lw, respectively. However, emerging brominated FRs such as decabromodiphenylethane (DBDPE), hexabromobenzene (HBB) and pentabromoethylbenzene (PBEB) were not detected in any sample. Bioaccumulation and bioconcentration processes were evaluated for the different families of compounds. Biomagnification factors (BMFs) were calculated, and some PBDE congeners (BDE-28, BDE-183 and BDE-209) as well as MeO-PBDEs presented BMF>1, being values of the naturally occurring MeO-PBDEs higher than those obtained for PBDEs. As regards halogenated norbornenes, BMF<1 were found.