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In the present study the occurrence of emerging hydrophobic organic pollutants in sediment samples from South America (Chile and Colombia) was investigated for the first time. Nineteen Chilean and thirteen Colombian sediment samples were analyzed in order to determine their content of brominated flame retardants (BFRs) (including PBDEs and emerging BFRs) as well as UV filters (UV-F). Samples were collected from neighboring aquatic ecosystems highly urbanized and industrialized in Colombia (Magdalena River area) and Chile (Biobio region). Different analytical procedures were applied depending on the selected analytes, based on chromatographic and mass spectrometric methodologies (GC-MS and LC-MS-MS). In general, concentration levels of both BFRs (up to 2.43 and 143ngg(-1) dw of PBDEs in Chile and Colombia, respectively) and UV-F (nd-2.96 and nd-54.4ngg(-1) dw in Chile and Colombia, respectively) were in the low range of published data, and the contribution of BFRs was higher than that of UV-F for almost all the sampled sediments., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

This paper documents the accumulation and emerging levels of Persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) found in the tissues of the migrating salmon species Oncorhynchus tshawytscha (Chinook salmon) in the Chilean Patagonia area. Even though salmon are not native to the southern hemisphere, reports indicate that Chinook salmon in the last few years have performed natural free-living style cycling, returning to rivers in the southern Patagonia area. Our study seeks to determine the presence and levels of PCB's and PBDE's in wild Chinook salmon in the northern part of the Chilean Patagonia, analyzing their relation with physiological parameters. Fish were sampled at the end of their entire life cycle when they returned to two principal rivers in the Aysen region in southern Chile. A number of fish (12) were sacrificed in situ and muscle samples were taken for PCBs measurements (sum 44 congeners) by gas chromatography electron capture detector (GC-ECD) and a number of PBDEs congeners, by gas chromatography mass spectrometry with negative chemical ionization detection (GC-MS NCI). Observed levels and patterns were characterized by concentrations of these POPs for PCBs ranging between 78 and 25.5 ng g(-1) wet weight and for PBDEs ranging between 272 and 1046 pg g(-1) wet weight, respectively. These ranges are among same levels reported in this same species in the northern hemisphere., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

Sediment cores from four Chilean lakes along the Andes Chain (Chungará, Laja, Castor and Venus) were analysed in order to investigate PCB concentrations and distributions in sediment samples. Sediment cores were analysed for PCBs using gas chromatography (GC-ECD/MS) and radioisotopically dated using 210Pb. Organic carbon content (OC) and 210Pb fluxes were also measured. Results showed that sediment PCB concentrations (ngg(-1) d.w.) at Lake Chungará (1.2 +/- 1) in northern Chile, Laja (5 +/- 4) in central, and in Lake Castor (3.5 +/- 4) in southern Chile (the eastern side of the Andes Mountain) were lower than sediments collected from Lake Venus (64 +/- 30) located in southern Chile (the western side) which contained 15-fold higher concentrations of PCBs. The percentage (%) of organic carbon was variable and showed a high range of values in the sediment fluctuating from 2% (Lake Laja) to 22% (Lake Chungará). Analysis of 210Pb fluxes, presented a decrease trend following Lake Laja>Castor>Chungará with a positive correlation with rainfall at each site. Sedimentation rates in Lake Castor (1846 gm(-2)yr(-1)) were higher than at Chungará (748 gm(-2)yr(-1)) and Lake Laja (508 gm(-2)yr(-1)). Focusing factor (FF) is used as a tool to elucidate PCB input in the aquatic ecosystem. FF were lower (<1) for the shallower lakes (Lakes Chungará and Castor). This study provides background levels of PCBs at remote lakes in Chile. Differences in geographical characteristics (orographic effect) might play an important role in the arrival of PCBs, particularly into the southern lakes. PCB fluxes indicated deposition of PCBs in recent sediments is higher than in previous years with peaks of PCB between 1991 and 1998. The continuing increase of PCB inputs in remote Chilean lakes, could be associated with long range atmospheric transport (LRAT).

Polybrominated diphenyl ethers (PBDEs) have become an issue of global concern. Recent studies have shown that farmed salmon can accumulate high levels of brominated compounds in their tissues and consequently there is a growing concern on its industrial and public health impacts. Little information is found in the international literature on PBDEs in the biotic compartment of the Southern Hemisphere. This paper reports the levels of several PBDE congeners found in the tissues of farmed fish from five different farming areas of Southern Chile. PBDEs were analyzed by HRGC-MS. More analytical data were obtained by analyzing these same pollutants in fish feed. Our results indicate a general trend of PBDE levels averaging 1.46 ng g(-1) wet weight (wwt). The observed congeneric distribution that resulted was quite similar to data previously reported in the open literature. PBDE profiles were found to be dominated by BDE 47. No correlation was observed between levels found in the tissues and the lipid content in such tissues, although a high correlation with the fish feed data was observed indicating that this could probably be the main PDBE entry source into fish, although other sources cannot be excluded. Even though the samples were obtained from different geographical areas, they presented fairly similar profiles, indicating a potential common source. We concluded that PBDE levels in the farmed Chilean salmon are in the low average range of values published in the open literature.

Schroederichthys chilensis is a common shark that lives in Chilean coastal environments. In this work, the relationship between liver 7-ethoxyresorufin-O-deethylase dealkylation (EROD) activity and Fluorescent Aromatic Compounds (FAC) in bile of S. chilensis sampled in three bays with different degrees of pollution were performed including a reference area. Sixty individuals were collected, 20 for each site; (10 males and 10 females per site) livers and bile samples were obtained and immediately frozen. EROD activity and FAC were measured according to three standard methods. EROD activity and FAC were higher in polluted areas than in the reference area. Synchronous Fluorescence Spectra of the bile from the fish collected at the most polluted area showed a peak at 347nm representing a metabolite corresponding to 1-hydroxypyrene. The low EROD activity in the reference area is likely related to the low level of PAH in sediments. We propose that this species is a good indicator of exposure to FACs, since it presents a series of characteristics that make it suitable for monitoring PAH exposure in coastal zones.

The Biobio River basin, located in central Chile, is one of the most important freshwater resources for a population of 1 million inhabitants. The river receives discharges of pulp mills, sewage treatment plants and there is a diffuse input of materials coming from the drainage basin. Previous studies reported high levels of etoxyresorufin-O-deethylase (EROD) induction in fish from the lower stretch of the river, mainly due to polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) exposure. The present study investigates polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) levels as well as EROD induction in fish livers from Central Chile's Biobio River. Dioxin and furan levels in fish livers are reported for the first time in three areas of the Basin. In all samples the highest concentrations were found for the octachlorodibenzo-p-dioxin (OCDD) and PCDD/F TEQ concentrations ranged from 2.83 to 6.33 ppt (wet weight). The results indicate a clear induction of EROD activity in different fish species as the river mouth is approached, although this induction is not clearly related with dioxin and furan levels found in the fish livers. Our results clearly show that other pollutants might be acting as EROD inductors in the Biobio Basin.

In this study the levels and distribution of some persistent toxic substances (PTS) were investigated in soils, superficial water, and snow along an altitudinal gradient in the Laja River Basin (South Central Chile). The principal objective was to establish the basin's contamination status. The working hypothesis was that PTS levels and distribution in the basin are dependent on the degree of anthropogenic intervention. Fifteen PAHs, seven PCBs congeners, and three organochlorine pesticides were studied in superficial soil and water samples obtained along the altitudinal gradient and from a coastal reference station (Lleu-Lleu River). Soil samples were extracted using accelerated solvent extraction with acetone/cyclohexane (1:1) for PAHs and organochlorine compounds. Contaminants were extracted from water and snow samples by liquid-liquid extraction (LLE). PAH and organochlorine compound quantification was carried out by HPLC with fluorescence detection and GC-MS, respectively. PCBs in soils presented four different profiles in the altitudinal gradient, mainly determined by their chlorination degree; these profiles were not observed for the chlorinated pesticides. In general, the detected levels for the analyzed compounds were low for soils when compared with soil data from other remote areas of the world. Higher summation operator PAHs levels in soils were found in the station located at 227 masl (4243 ng g-1 TOC), in a forestry area and near a timber industry, where detected levels were up to eight times higher than the other sampling sites. In general, PAH levels and distribution seems to be dependent on local conditions. No pesticides were detected in surface waters. However, congeners of PCBs were detected in almost all sampling stations with the highest levels being found in Laja Lake waters, where 1.1 ng/l were observed. This concentration is two times higher than values reported for polluted lakes in the Northern Hemisphere. The presence of organochlorine compound in snow sampled at the highest elevation point of the basin is indicative of the transport and atmospheric deposition phenomena of alpha-HCH, gamma-HCH and PCB 52, with values being similar to the levels reported in Canadian snow samples. We conclude that environmental PTS substance levels are in general relatively low, although PAHs may be of concern in some areas of the basin.

Residues of five pesticides in surface water were surveyed during 2001 and 2003 in the Traiguen river basin in Southern Chile. Simazine, hexazinone, 2,4-D, picloram herbicides and carbendazim fungicide were selected through a pesticide risk classification index. Six sampling stations along the river were set up based on agricultural and forestry land use. The water sampling was carried out before and after the pesticide application periods and in correspondence to some rain events. Pesticides were analyzed by HPLC with DAD detection in a multiresidue analysis. During 2001, in the first sampling campaign (March), the highest concentrations of pesticides were 3.0 microg l(-1) for simazine and hexazinone and 1.8 microg l(-1) for carbendazim. In the second sampling (September), the highest concentration were 9.7 microg l(-1) for 2,4-D, 0.3 microg l(-1) for picloram and 0.4 microg l(-1) for carbendazim. In the last sampling period (December), samples indicated contamination with carbendazim fungicide at levels of up to 1.2 microg l(-1). In sampling carried out on May 2003, no pesticides were detected. In October 2003, the highest concentrations of pesticides were 4.5 microg l(-1) for carbendazim and 2.9 microg l(-1) for 2,4-D. Data are discussed in function of land use and application periods of the products, showing a clear seasonal pattern pollution in the Traiguen river. Risk assessment for these pesticides was calculated by using a risk quotient (RQ = PNEC/PEC). For picloram the calculated RQ < was 0, which indicates that no adverse effects may occur due to the exposure to this herbicide in the Traiguen river basin. For 2,4-D, simazine, hexazinone, carbendazim RQ > 1, meaning that adverse effects could occur and it is necessary to reduce pesticide exposure in surface waters. It is recommended to continue with a pesticide monitoring program and the implementation of ecotoxicological testing with local and standardized species in order to consider the probability of effects occurrence, with less uncertainty. Thus, it will be more feasible to make some recommendations to regulatory agencies regarding the pesticide use.

This paper documents the occurrence of polychlorinated biphenyl (PCB) and hexachlorocyclohexane (HCH) deposition inferred from a sedimentary record exposed in a salt-marsh trench in South-Central Chile. Sediments were carefully collected every 1 cm from the trench wall. The samples were analyzed for PCBs, HCHs, 137Cs, organic carbon and grain size. The 137Cs fallout and the sedimentary signature left by the 1960 Chilean tsunami were used as temporal markers to estimate the stratigraphic chronology and the sedimentation rates. PCBs were quantified by gas chromatography with electron capture detection (GC-ECD), and positive samples were confirmed by gas chromatography and mass spectrometry detection (GC-MS). Based on these results, PCBs and HCHs deposition over the last 40 years was estimated. No PCBs were detected below the tsunami signature. Total concentrations ranged from undetectable (ND) to 32 ng/g d.w. for PCBs and from undetectable (ND) to 1.29 ng/g d.w. for HCHs. The highest PCB concentrations were found in the upper 7 cm of the core. Even though PCBs were banned in 1982 as electrical fluids in Chile, total estimated PCB fluxes have increased approximately 20 times during the last 40 years: from undetectable values to 102.6 ng/cm2/year, reflecting that PCBs are still in use and being released into the environment.

This paper presents a first report on chlorinated pesticide deposition analyzed through sedimentary records in a small mesotrophic lake (Chica de San Pedro) in central Chile. The sediment core was sliced and dated using 210Pb, 137Cs and pollen analyses. Organochlorine pesticides were analyzed by gas chromatography with electron capture detection (GC-ECD). From these results, pesticide deposition over the last 50 years was estimated. No pesticides were detected below the 1940 slice of the core. Concentrations were in the range 0.640-1.4 ng/g d.w. for total DDTs, 0.046-0.362 ng/g d.w. for lindane and 0.015-0.310 ng/g d.w. for alpha-hexachlorohexane. Highest concentrations of pp'DDT were found in 1993-1996 and higher concentrations of pp'-DDE and pp'-DDD were found in the seventies (1972-1978). Total organic carbon (TOC) normalized data were used for statistical analysis. Although significant correlation was observed between concentrations of DDE and DDD, no correlation was found for DDT, suggesting that it had a different source. Factorial analysis grouped DDE together with DDD, while DDT was grouped together with gamma- and alpha-HCH. Total DDT fluxes were highest during the 1970s, while those for HCHs have been increasing in the 1990s. In Chile, organochlorine compounds were banned in 1985, and the historical deposition patterns seem to indicate that such measures have been effective. On the other hand, results point out a relatively new occurrence of pp'-DDT in the watershed, but the source remains unknown.

Cytochrome P450-dependent monooxygenase (MFO) activity and levels of bile PAH metabolites were measured in fish (Oncorhynchus mykiss) exposed to Biobio river (Chile) water. Experiments were performed simultaneously in both the field and laboratory to investigate whether the river water contained notable bioavailable PAH fractions. The field experiment was conducted using fish caged for 41 days at La Mochita (Biobio river mouth) whereas the laboratory experiment involved a 21-day exposure treatment with water collected in the same area. Induction of hepatic MFO, assayed by benzo(a)pyrene monooxygenase activity (BaPMO), and levels of PAH metabolites in the bile were measured in groups of eight (field experiment) and four specimens (laboratory experiment) sampled after 5, 10, 21 and 41 days of exposure. BaPMO was induced by a factor of 23 and 25 in fish caged for 21 and 41 days, respectively. Likewise, a significant BaPMO induction was found in the fish group experimentally exposed to river water for 21 days. Biliary fluorescence measurements, recorded by fixed wavelength fluorescence (FF) and synchronous fluorescence spectroscopy (SFS), revealed significantly high levels of PAH metabolites in bile samples of fish caged for 21 and 41 days. A positive relationship was found between BaPMO activity and biliary PAH metabolites. This study provides evidences that (i) Biobio river water contains a significant bioavailable PAH fraction in terms of marked effects on fish and (ii) the biological indicators MFO activity and bile PAH metabolites represent an excellent screening methodology to assess PAH exposure.