Occurrence and air-water diffusive exchange legacy persistent organic pollutants in an oligotrophic north Patagonian lake.

In this study, the occurrence and diffusive air-water exchange of POPs in Panguipulli Lake (39°42'S-72°13'W), an oligotrophic lake located in northern Patagonia (Chile), were determined. Air and water samples were collected between March and August 2017 (autumn-winter) and analyzed for concentrations of OCPs (α-HCH, ß-HCH, γ-HCH and HCB) and PCBs (PCB-28,-52,-101,-118,-153,-158,-180) using gas chromatography coupled with an electron capture detector. The direction of air-water exchange direction was evaluated using a fugacity approach (ƒw ƒa-1), and net diffusive exchange fluxes (FAW, ng m-2 d-1) were also estimated. Total ∑4OCP levels in air ranged from 0.31 to 37 pg m-3, with a maximum for ß-HCH, while Σ7PCB levels ranged from 3.05 to 43 pg m-3. The most abundant congener was PCB-153, accounting for 60% of the total PCBs in air. Surface water ∑4OCPs measured in this study ranged from 1.01 to 3.9 pg L-1, with γ-HCH predominating, while surface water Σ7PCB levels ranged from 0.32 to 24 pg L-1, with PCB-101, PCB-118, and PCB-153 presenting the highest levels. Diffusive air-water exchanges of HCB, α-HCH, γ-HCH and PCBs in the form of volatilization from the lake to air predominated; in contrast, for ß-HCH net deposition dominated during the sampling period. Estimates suggested faster microbial degradation in the dissolved phase compared to atmospheric degradation for all analyzed POPs. Overall, these results could indicate that the oligotrophic lakes of northern Patagonia act as a secondary source of atmospheric POPs, mainly PCBs and some OCPs. This study is a first attempt to understand the occurrence of POPs in air and water, as well as their dynamics in oligotrophic lakes in the southern hemisphere.

Toxic effects of antiparasitic pesticides used by the salmon industry in the marine amphipod Monocorophium insidiosum.

The use of antiparasitic pesticides (APs) has been widely required by the salmon industry to treat diseases. The direct emission of chemicals in the seawater has produced uncertainty about the potential effects on nontarget organisms, such as crustaceans. The aim of this study was to assess the toxicity of three APs used by the salmon farm industry, such as emamectin benzoate (EB), cypermethrin (CP), and deltamethrin (DE), in the amphipod Monocorophium insidiosum during 10 days through whole-sediment bioassay tests. Lethal concentration by 50 % (LC50-10d) and biochemical responses, such as glutathione S-transferase (GST) and thiobarbituric acid reactive substances (TBARS), were measured as exposure and effects end points, respectively. Acute assays for DE (7.8 µg kg(-1), confidence interval, CI95% 5-11) and CP (57 µg kg(-1), CI95% 41-77) showed more mortality than EB (890 µg kg(-1), CI95% 672-1,171). In this study, it was possible to observe sublethal responses in amphipods after 2 days of exposure to APs. Significant induction in GST and TBARS (p < 0.05) were measured for CP and EB. Lower DE concentrations showed no significant biochemical responses. M. insidiosum was sensitive to AP concentrations at µg kg(-1) in sediments. This information would allow considering the possible consequences of detected concentrations for APs in areas with intensive salmon farming activity.

Multicompartmental analysis of POPs and PAHs in Concepciόn Bay, central Chile: Part II - Air-sea exchange during Austral summer.

Air-sea exchange of POPs and PAHs was assessed in Concepción Bay during January, summer 2015. Results showed low levels, in air and water, for POPs (1-20 pg m-3, and 6-50 pg L-1, respectively) and for ΣPAHs (1-2 ng m-3 and 1-2 ng L-1, respectively). The highest levels were found for PBDEs (200-20,000 pg L-1) in the water samples (3-fold times higher than PCBs and OCP) and PBDE209 accounted for 90% of total ΣPBDEs. Air-sea exchange fluxes (ng m-2 d-1) were low in general, with exception of PBDEs showing values up to 40,000 ng m-2 d-1. Net deposition was found for PAHs, HCB and some PBDEs; while, BDE99, and BDE100 showed net volatilization. These findings contribute with new data of diffusive air-sea exchange on the southern hemisphere Pacific coast.

Antibiotics florfenicol and flumequine in the water column and sediments of Puyuhuapi Fjord, Chilean Patagonia.

Chile is a major global producer of farmed salmon in the fjords of Patagonia, and therefore a major consumer of antibiotics. We tested whether the antibiotics florfenicol and flumequine persisted in the large Puyuhuapi Fjord after the six months following mandatory concerted treatment by all salmon farms present in the fjord. Antibiotics were detected in 26% of analyzed samples, but only within the particulate phase, with concentrations of florfenicol of up to 23.1 ng L-1, where detected. Flumequine was present in one sample at trace concentration, and neither antibiotic was detected in the dissolved phase nor in surface sediments. A fugacity-based model predicted that flumequine should theoretically remain in surface sediments at the sub-Minimal Inhibiting Concentrations (sub-MIC) previously shown to promote selection for antibiotic resistance in bacteria. Our observations suggest that surface sediments might act as a reservoir for antibiotic resistomes of bacteria, and that bacteria bearing antibiotic resistance genes could eventually become a risk for human health through the consumption of marine products.

Assessing the ecological risk of active principles used currently by freshwater fish farms.

The global aquaculture industry has grown exponentially in recent years using to control of infections and diseases, a variety of veterinary drugs (VMP) are used, including antibiotics, antifungals and antiparasitics, which have different routes of emission, environmental persistence and side effects to aquatic organisms, becoming one of the main concerns in its use of veterinary drugs (VMP) and its potential toxicological impact on the environment, in this context, Chile is considered one of the main salmon producers. Ecological risk assessment of active principles used infreshwater fish farms worldwide and in Chile were investigated. We recollect a physical - chemical properties of active principles used by fish farms and we could estimate the relative hazard a priori. Later active principles grouped as antibiotics (n = 6), antiparasitics (n = 5), anesthetics (n = 3), and disinfectants (n = 7) were assessed using a mass balance model based on fugacity was developed for each active principle under treatments via immersion and food administration in fish, while a volumetric model for disinfectants and sodium chloride was used for estimating the predicted environmental concentration (PEC), under a real smolt farming scenario in fish farms. Ecotoxicological data were collected from open literature to predict the no-effect concentration (PNEC). The ecological risk assessment was characterized using a risk quotient (RQ = PEC/PNEC) based in two assessment tiers. Results revealed that 12 active ingredients showed a high risk (RQ ≥ 1), thus indicating that adverse effects could occur and further investigation with measured concentrations in the field are required to reduce exposure in surface waters.

Endocrine Disruptor Impacts on Fish From Chile: The Influence of Wastewaters.

Industrial wastewaters and urban discharges contain complex mixtures of chemicals capable of impacting reproductive performance in freshwater fish, called endocrine-disrupting compounds (EDCs). In Chile, the issue was highlighted by our group beginning over 15 years ago, by analyzing the impacts of pulp and paper mill effluents (PPME) in the Biobio, Itata, and Cruces River basins. All of the rivers studied are important freshwater ecosystems located in the Mediterranean region of Central Chile, each with a unique fish biodiversity. Sequentially, we developed a strategy based on laboratory assays, semicontrolled-field experiments (e.g., caging) and wild fish population assessments to explore the issue of reproductive impacts on both introduced and native fish in Chile. The integration of watershed, field, and laboratory studies was effective at understanding the endocrine responses in Chilean freshwater systems. The studies demonstrated that regardless of the type of treatment, pulp mill effluents can contain compounds capable of impacting endocrine systems. Urban wastewater treatment plant effluents (WWTP) were also investigated using the same integrated strategy. Although not directly compared, PPME and WWTP effluent seem to cause similar estrogenic effects in fish after waterborne exposure, with differing intensities. This body of work underscores the urgent need for further studies on the basic biology of Chilean native fish species, and an improved understanding on reproductive development and variability across Chilean ecosystems. The lack of knowledge of the ontogeny of Chilean fish, especially maturation and sexual development, with an emphasis on associated habitats and landscapes, are impediment factors for their conservation and protection against the threat of EDCs. The assessment of effects on native species in the receiving environment is critical for supporting and designing protective regulations and remediation strategies, and for conserving the unique Chilean fish biodiversity.

Sources and diffusive air-water exchange of polycyclic aromatic hydrocarbons in an oligotrophic North-Patagonian lake.

Polycyclic aromatic hydrocarbons (PAHs) are semivolatile organic compounds of environmental concern. This study aims to investigate the influence of local sources of anthropogenic PAHs and their air-water exchange fluxes in an oligotrophic North-Patagonian lake in Chile. The monitoring was carried out in Panguipulli Lake during a six-month period during the autumn and winter seasons (March to August 2017) using a high-volume air sampler and a pump system for water samples. We detected and quantified fifteen PAHs in the gas phase (mean ∑15PAHs = 11.6 ng m-3) and dissolved water phase (mean ∑15PAHs = 961.8 pg L-1). Methylphenanthrenes and pyrene dominated the concentrations of PAHs in the studied phases. To determine sources of PAHs we used the PAH ratios of Light Molecular Weight/Heavy Molecular Weight (∑LMW/∑HMW) and Phenanthrene/Anthracene (Phe/Ant). The PAH ratio results revealed a pyrogenic source. We estimated the air-water diffusive exchange fluxes and fugacity ratios for the studied compounds. In general, air-water diffusive exchanges of PAHs showed a net volatilization for the less hydrophobic (log KOW < 4) and lighter PAHs (MW ≤ 170 g mol-1), and a net deposition trend for the more hydrophobic (log KOW 4-7) and higher molecular weight PAHs (MW ≥ 178 g mol-1). We found a significant correlation between log water/air fugacity ratios and log KOW of PAHs. Therefore, it is suggested that this oligotrophic lake acts as a sink by accumulating hydrophobic and mid-high molecular weight PAHs derived mainly from pyrogenic sources. This study is the first attempt to understand the sources and behavior of PAHs in oligotrophic lakes in the Southern Chile where information is scarce regarding the occurrence of PAHs.

Development of an analytical methodology for the determination of organochlorine pesticides by ethylene-vinyl acetate passive samplers in marine surface waters based on ultrasound-assisted solvent extraction followed with headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry.

A novel strategy for the analysis of 20 organochlorine pesticides (OCPs) monitoring in marine surface waters through ethylenevinyl acetate (EVA) passive samplers was developed and validated. The approach is based on the coupled of ultrasound-assisted solvent extraction (UASE) and headspace solid-phase microextraction (HS-SPME) as extraction method for OCPs from EVA samplers. The UASE-HS-SPME method was optimized with a 27-4 Plackett-Burman design, while the significant factors (salting out, temperature and extraction time) were optimized using a central composite design (CCD) combined with desirability function (DF). The OCPs detection was performed using multiple reaction monitoring (MRM) by gas chromatography-tandem mass spectrometry (GC-MS/MS). The optimum experimental conditions comprised: salting out: 23% wv-1 NaCl, temperature: 75°C and extraction time: 55 min. The optimized method was validated in terms of linearity (R2>0.9946), recovery (>61%) and inter-day and intra-day reproducibility (<19%) for 20 OCPs studied. The limits of detection (LODs) were ranging from 0.01 ng for α-hexachlorocyclohexane and 0.27 ng for endrin aldehyde. Finally, the methodology was tested in marine surface seawater of Southern Chile using EVA samplers, where twelve OCPs were detected at ultra-trace levels (ngL-1).

Occurrence of antiparasitic pesticides in sediments near salmon farms in the northern Chilean Patagonia.

Growth of the aquaculture industry has triggered the need for research into the potential environmental impact of chemicals used by salmon farms to control diseases. In this study, the antiparasitic pesticides emamectin benzoate (EB), diflubenzuron (DI), teflubenzuron (TE), and cypermethrin (CP) were measured in sediments near salmon cages in southern Chile. Concentrations for EB were between 2.2 and 14.6ngg-1, while the benzoylphenyl ureas DI and TE were detected in the ranges of 0.1 to 1.2ngg-1 and 0.8 to 123.3ngg-1, respectively. These results were similar to data reported for the Northern Hemisphere. On the other hand, the pyrethroid CP was detected in higher concentrations, ranging from 18.0 to 1323.7ngg-1. According to reported toxicity data, this range represents a potential risk for benthic invertebrates. This report is the first baseline attempt at assessing antiparasitic pesticide levels in the Chilean Patagonia.

Passive samplers of hydrophobic organic chemicals reach equilibrium faster in the laboratory than in the field.

The use of passive sampling methods for monitoring hydrophobic organic chemicals frequently requires the determination of equilibration times and partition coefficients in the laboratory. These experiments are often carried out by exposing passive samplers in a finite water volume, and errors are easily made when the obtained results are applied to the field, where water volumes are essentially infinite. The effect of water volume on the equilibration rate constant is discussed, using a mechanistic model. Application of this model to two literature reports illustrates that aqueous concentrations in the field may be underestimated by a factor of 10 or more, when the water volume effect is neglected. Finally, it is shown that the concept of "sorption capacity" (sampler mass times partition coefficient) allows for a more intuitive understanding of the passive sampling process in small and large water volumes, which may reduce the risk of laboratory-field extrapolation errors.

Ethylene vinyl acetate polymer as a tool for passive sampling monitoring of hydrophobic chemicals in the salmon farm industry.

Current monitoring programs are focused on hydrophobic chemicals detection in aquatic systems, which require the collection of high volumes of water samples at a given time. The present study documents the preliminary use of the polymer ethylene vinyl acetate (EVA) as a passive sampler for the detection of a hydrophobic chemical used by salmon industries such as cypermethrin. Initially, an experimental calibration in laboratory was performed to determine the cypermethrin equilibrium between sampler and aquatic medium, which was reached after seven days of exposure. A logarithm of partitioning coefficient EVA-water (logKEVA-W) of 5.6 was reported. Field deployment of EVA samplers demonstrated average concentrations of cypermethrin in water to be 2.07 ± 0.7 ng L(-)(1) close to salmon cages, while near-shore was 4.39 ± 0.8 ng L(-)(1). This was a first approach for assessing EVA samplers design as a tool of monitoring in water for areas with salmon farming activity.

Health status of native fish (Percilia gillissi and Trichomycterus areolatus) downstream of the discharge of effluent from a tertiary-treated elemental chlorine-free pulp mill in Chile.

Few data exist on the possible effects of pulp and paper effluent discharge on native fish populations in the Southern Hemisphere, relative to the research done in the Northern Hemisphere. The present research examined two native fish species (Trichomycterus areolatus and Percilia gillissi) for effects at both the molecular and individual level due to the discharge of effluent from a tertiary treated elemental chlorine-free pulp mill into a fluvial system in Central Chile over three seasons (February 2007, October 2007, January 2008). Different responses were observed between species and between sexes. There was an increase in the production of gonadal 17ß-estradiol in the females of both species but a drop in 11-ketotestosterone production in P. gillissi males. Female gonadal size was increased, especially during the summer period, with corresponding increases the frequency of advanced oocyte development, and in the oocyte diameter in both species. Hepatic ethoxyresorufin-O-deethylase (EROD) activity was elevated for both species downstream of the discharge point, although overall it was higher in P. gillissi than T. areolatus. Decreases in the frequency of smaller-sized fish for both species, as well as a drop in the size of the adults downstream of the discharge point, were observed. The present study is the first evidence of endocrine disruption in native freshwater fish associated with modern pulp mills in South America. This study establishes possible links in the reproductive alterations observed at the subindividual and individual levels that could explain the changes observed at the population level.