Passive-Sampler-Derived PCB and OCP Concentrations in the Waters of the World─First Results from the AQUA-GAPS/MONET Network.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

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.

Integrated Physiological Biomarkers Responses in Wild Fish Exposed to the Anthropogenic Gradient in the Biobío River, South-Central Chile.

To evaluate the physiological state of the wild fish inhabiting the Biobío River in South-Central Chile, susceptible to the chemical contamination from different sources, biochemical and physiological biomarkers were applied to wild fish Percilia irwini and Trichomycterus areolatus in situ. Fish caught in the Biobío river in low, medium, and high anthropic impacts areas, with different pollution degrees along the river. Ethoxyresorufin O-O deethylase (EROD) activity was evaluated in fish liver. Length, weight, Gonad weight and Liver weight, Physiological Index, and gill and liver histopathology were conducted. Physicochemical parameters (pH, Temperature, Conductivity, and TDS) were measured at each sampling site. The results indicated a deteriorating condition in the biological parameters of both species in a high anthropic zone. Fishes show an increase in physiological indices and EROD liver activity, agreeing with previous studies supporting evidence of reproductive change development as we move downstream the river. Also, an increase in histopathological lesions towards the lower third stretch of the Biobío River. The Integrated Index of Physiological Biomarkers (IPBR) indicated that sites located in the high impact area (P. irwini: BC: 4.09; RC: 3.38; PC: 3.50; SJ: 2.34 and T. areolatus BC: 6.06, PC: 5.37; SJ: 5.42) have the most detrimental environmental quality, compared to reference area. The integrated biomarker analysis demonstrates that the alterations observed are related to the high anthropic activity levels downstream from the sites with the least intervention, demonstrating that the IPBR used is a complementary tool for studies of the Environmental Effects Monitoring approach.

Assessing wild fish exposure to ligands for sex steroid receptors from pulp and paper mill effluents in the Biobio River Basin, Central Chile.

Bioactive substances in the Biobio River Basin in Chile were examined by deploying Semi Permeable Membrane Devices (SPMDs) upstream and downstream of 4 pulp mill effluent discharges. Androgenic and estrogenic activity of SPMD extracts were then evaluated using in vitro fish sex steroid receptor binding assays. The results indicated the occurrence of estrogenic type compounds associated with one of the mill discharges. A significant correlation among the presence of these compounds, an increase in gonadosomatic index GSI and induction of hepatic EROD activity of two native fish species was observed. However, no significant presence of mature oocytes in female gonads was detected. Although EROD induction was observed in sites impacted by mill effluents, an increase of its activity occurred towards the downstream areas, suggesting other non-mill sources. More research is needed to understand the environmental changes in context of the new technological improvements in treatment systems to MBBR (Moving Bed Biofilm Reactor) recently implemented by the pulp mill industries.

A Global Overview of Exposure Levels and Biological Effects of Trace Elements in Penguins.

Trace elements are chemical contaminants that can be present almost anywhere on the planet. The study of trace elements in biotic matrices is a topic of great relevance for the implications that it can have on wildlife and human health. Penguins are very useful, since they live exclusively in the Southern Hemisphere and represent about 90% of the biomass of birds of the Southern Ocean. The levels of trace elements (dry weight) in different biotic matrices of penguins were reviewed here. Maps of trace element records in penguins were included. Data on exposure and effects of trace elements in penguins were collected from the literature. The most reported trace elements in penguins are aluminum, arsenic, cadmium, lead, mercury, copper, zinc, and manganese. Trace elements have been measured in 11 of the 18 species of penguins. The most studied biotic matrices are feathers and excreta. Most of the studies have been performed in Antarctica and subantarctic Islands. Little is known about the interaction among metals, which could provide better knowledge about certain mechanisms of detoxification in penguins. Future studies of trace elements in penguins must incorporate other metals such as vanadium, cobalt, nickel, and chromium. Data of metals in the species such as Eudyptes pachyrhynchus, Eudyptes moseleyi, Eudyptes sclateri, Eudyptes robustus, Eudyptes schlegeli, Spheniscus demersus, Spheniscus mendiculus, and Megadyptes antipodes are urged. It is important to correlate levels of metals in different biotic matrices with the effects on different species and in different geographic locations.

Embryo-larvae and juvenile toxicity of Pb and Cd in Northern Chilean scallop Argopecten purpuratus.

This study aimed to investigate the effects of Cd and Pb on earlier stage of the commercially important scallop (Argopecten purpuratus) in the contamination context of Northern Chile where this specie is farmed, through acute exposure bioassays in embryo-larvae measuring cumulative abnormality (EC50) and juvenile cumulative mortality (LC50) as endpoints, based on environmentally detected concentrations and available toxicological data from similar species. Embryo-larvae exposure indicates 48 h EC50 of 1.55 mg/L Cd, and 0.044 mg/L Pb. On the contrary, 96 h LC50 in juvenile scallops was 0.48 mg/L Cd and 1.47 mg/L Pb. Our results demonstrated differential toxicity between embryo and juvenile scallops that might relate to different primary defense mechanisms or effect in morphological development of individuals in each ontogenetic stage. Compared to similar bivalve metal toxicity tests, this study demonstrated that A. purpuratus embryos are more sensitive to Pb than most other bivalve species. Our results indicate that maximum permitted levels of Pb in marine waters and estuaries (according to Chilean regulation) could pose a risk for scallops' first stage of life (embryo-larvae) development, and needs to be reviewed. Furthermore, Chilean environmental regulations do not have quality standards for marine sediments (currently under discussion), where high levels of metals have been continuously reported.

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.

Assessment of trace metals and porphyrins in excreta of Humboldt penguins (Spheniscus humboldti) in different locations of the northern coast of Chile.

To add data on trace metal contamination of Humboldt penguins in the South Pacific, levels of trace metals (As, Hg, Pb, Cu, Zn, and Cd) and porphyrins (copro-, uro-, and proto-) in excreta of Humboldt penguins that inhabit some important nesting sites on the northern coast of Chile were determined. Fresh excreta were collected on Pan de Azúcar Island, Chañaral Island, and Cachagua Island, from December 2011 to January 2012. Concentration of metals was determined by flame atomic absorption spectrophotometry, whereas porphyrins levels were measured by fluorimetric analysis. Concentrations (dry weight) of Cu (199.67 µg g(-1)), As (7.85 µg g(-1)), and Pb (12.78 µg g(-1)) were higher (p ≤ 0.05) in Cachagua Island. Colonies from Pan de Azúcar Island showed the highest levels of Hg (0.76 µg g(-1)), Cd (47.70 µg g(-1)), and Zn (487.10 µg g(-1)). Samples from Cachagua Island showed the highest (p ≤ 0.05) levels of copro- (2.16 nmol g(-1)), uro- (2.20 nmol g(-1)), and protoporphyrins (2.23 nmol g(-1)). There was a positive correlation between the metals As, Pb, and Cu with uro-, copro-, and protoporphyrins. The results indicated that penguin colonies from Cachagua Island are more exposed to metal contamination than penguin colonies from Pan de Azúcar and Chañaral Islands, thus being more likely to develop certain diseases caused by contamination with metals. Considering biomagnification, the metals detected in the excreta of Humboldt penguins can be a source of contamination from marine environments to terrestrial ecosystems, which could also affect other living organisms.

Groundwater Leaching Potential of Pesticides: A Historic Review and Critical Analysis.

We evaluated the main leaching indices that have been used for decades for the protection of groundwater against contamination by pesticides. We describe the index classifications in detail and discuss their advantages and limitations relative to their prediction value. Most of the indices have similarities in the types of parameters they use. Some of the similarities are basic physicochemical properties of the pesticides such as their water solubility and their organic carbon partition coefficient, as well as characteristics such as environmental persistence in the soil and some soil characteristics. It is very difficult to maintain a simple index with high predictive power. However, comparisons are allowed by many indices among different active ingredients before pesticides are classified according to the risk of being groundwater contaminants. In contrast, limitations are the scarce inclusion of pesticide byproducts in the ground, lack of prediction capacity for polar pesticides, and lack of prediction of the vulnerability of groundwater to being contaminated by pesticides. Despite the limitations of such approaches, they are of great utility, particularly for protection of groundwater from pesticide contamination when little information is available, which is the case in most developing countries and in countries with economies in transition. Caution is recommended in the analysis of information generated by these approximations, which ideally should be validated experimentally in the different application scenarios and the needs for pesticide assessment based on local information. Environ Toxicol Chem 2024;00:1-14. © 2024 SETAC.

Assessing ammonium pollution and mitigation measures through a modified watershed non-point source model.

Watershed water quality modeling is a valuable tool for managing ammonium (NH4+) pollution. However, simulating NH4+ pollution presents unique challenges due to the inherent instability of NH4+ in natural environment. This study modified the widely-used Soil and Water Assessment Tool (SWAT) model to simulate non-point source (NPS) NH4+ processes, specifically incorporating the simulation of land-to-water NH4+ delivery. The Jiulong River Watershed (JRW) is the study area, a coastal watershed in Southeast China with substantial sewage discharge, livestock farming, and fertilizer application. The results demonstrate that the modified model can effectively simulate the NPS NH4+ processes. It is recommended to use multiple sets of observations to calibrate NH4+ simulation to enhance model reliability. Despite constituting a minor proportion (5.6 %), point source inputs significantly contribute to NH4+ load at watershed outlet (32.4∼51.9 %), while NPS inputs contribute 15.3∼17.3 % of NH4+ loads. NH4+ primarily enters water through surface runoff and lateral flow, with negligible leaching. Average NH4+ land-to-water delivery rate is about 2.35 to 2.90 kg N/ha/a. High delivery rates mainly occur at agricultural areas. Notably, proposed NH4+ mitigation measures, including urban sewage treatment enhancement, livestock manure management improvement, and fertilizer application reduction, demonstrate potential to collectively reduce the NH4+ load at watershed outlet by 1/4 to 1/3 and significantly enhance water quality standard compliance frequency. Insights gained from modeling experience in the JRW offer valuable implications for NH4+ modeling and management in regions with similar climates and significant anthropogenic nitrogen inputs.

Biochemical and behavioral responses in the estuarine polychaete Perinereis gualpensis (Nereididae) after in situ exposure to polluted sediments.

In situ translocation experiments are advantageous relative to traditional laboratory experiments, particularly for understanding the bioavailability of trace metals like mercury (Hg). Individuals of the polychaete Perinereis gualpensis were translocated from a reference site (Raqui estuary, Chile) to an estuarine site with significant sediment Hg concentrations (Lenga estuary: 1.78-9.89 mg/kg). Individuals were exposed in polluted and non-polluted sediments for 21 days and sampled every 7 days with cages deployed at three different depths. Tissue Hg concentrations were measured in conjunction with oxidative stress responses. Translocated polychaetes rapidly accumulated Hg. Glutathione S-transferase (GST) activities measured from posterior body regions were 2-fold higher than control activities after 21 days of exposure. Other antioxidant measures were idiosyncratic. Distinct burrowing behavior differences were observed; control polychaetes exhibited more homogenous vertical distributions, whereas in Lenga, worms tended to remain in upper layers. These studies demonstrate that under natural conditions, Hg is highly bioavailable to polychaetes affecting both biochemical and behavioral responses after relatively short-term exposure.

Assessment and optimization of an ultrasound-assisted washing process using organic solvents for polychlorinated biphenyl-contaminated soil.

The goal of this work was to evaluate a washing process that uses organic solutions for polychlorinated biphenyl (PCB)-contaminated soil, and includes an ultrasound pre-treatment step to reduce operational times and organic solvent losses. In a preliminary trial, the suitability of 10 washing solutions of different polarities were tested, from which three n-hexane-based solutions were selected for further evaluation. A second set of experiments was designed using a three-level Taguchi L27 orthogonal array to model the desorption processes of seven different PCB congeners in terms of the variability of their PCB concentration levels, polarity of the washing solution, sonication time, the ratio washing solution/soil, number of extraction steps and total washing time. Linear models were developed for the desorption processes of all congeners. These models provide a good fit with the results obtained. Moreover, statistically significant outcomes were achieved from the analysis of variance tests carried out. It was determined that sonication time and ratio of washing solution/soil were the most influential process parameters. For this reason they were studied in a third set of experiments, constructed as a full factorial design. The process was eventually optimized, achieving desorption rates of more than 90% for all congeners, thus obtaining concentrations lower than 5 ppb in all cases. The use of an ultrasound-assisted soil washing process for PCB-contaminated soils that uses organic solvents seems therefore to be a viable option, especially with the incorporation of an extra step in the sonication process relating to temperature control, which is intended to prevent the loss of the lighter congeners.

Liver ethoxyresorufin-O-deethylase and brain acetylcholinesterase in two freshwater fish species of South America; the effects of seasonal variability on study design for biomonitoring.

Responses at low levels of biological organization to evaluate environmental changes and water quality have been used for many years. South America is no different, and recently biochemical endpoints in fish have been used to assess the impacts of industrial and sewage effluents on wild fish populations. For Chilean native freshwater fish, basic biological data is scarce and data on 7-ethoxyresorufin-O-deethylase (EROD) and Acetylcholinesterase (AChE) activity is practically absent. Moreover, extensive variation in these two biochemical endpoints exists among species and seasons. In this article we evaluate seasonal variation in liver EROD and brain AChE activities in Trichomycterus areolatus and Percilia gillissi, two widely distributed native freshwater fish species in central Chile. We observed a marked seasonality in hepatic EROD activity in both species, with maximums for P. gillissi during winter months and sex differences in February, July, August and December. T. areolatus showed no sex differences, and peaks in EROD activity in the middle of summer, winter and late spring. Species differences in EROD activity were observed with activity being 1-2 orders of magnitude higher in P. gillissi compared to T. areolatus. Scarce seasonal variation and no sex related differences in brain AChE for both species were observed. Multivariate analysis (PCA) indicated that physical water quality parameters had some degree of responsibility for the seasonal responses found. The seasonal variability data of these biochemical endpoints were used to optimize study design for future monitoring programs, planning timing of sampling, increasing statistical power by collecting specific sample sizes required.

Polybrominated diphenyl ether levels in wild and farmed Chilean salmon and preliminary flow data for commercial transport.

This pilot study documented the occurrence and levels of brominated flame retardants in the tissues of farmed and wild salmon in southern Chile. Samples of Coho salmon and rainbow trout were obtained from fish farms, rivers and lakes in the Patagonia in Aysen Region, Chile. The samples were analyzed by Gas Chromatography Negative Chemical Ionization Mass Spectrometry for the different polybrominated diphenyl ether (PBDE) congeners. Contaminants were observed in all the samples, and the congeners BDE 17, 28, 47 and 66 were observed in all both farmed and wild samples. The concentrations were higher in the farmed Coho salmon, presenting significant differences with wild salmon. The levels reached 182 pg/g wet weight (ww) vs. 120 ww. In the case of the rainbow trout, the concentrations were lower, although the congener profile was quite similar. The levels reached an average of 100 pg/g ww in the farmed fish versus 110 pg/g ww in wild fish, and no significant difference was observed between the species. In both species, the congener with the highest concentration was BDE 47. Based on this information, the BDE flow was estimated for commerce, which is a form of pollutant transport not usually considered in POP pollution studies. A preliminary estimation indicated that the quantity of PBDEs mobilized by commerce was in the order of kg, and in the case of Chile might reach almost 1 kg.

[Quality indicators for blood culture: three years of monitoring at a university hospital in Chile]. / Análisis de la monitorización de cinco indicadores de calidad del hemocultivo en un hospital universitario en Chile 2009-2011.

Blood culture is considered the "gold standard" for the diagnosis of bacteremia, critical condition with high morbidity and mortality. Because of its importance, it is estimated that the blood culture is a critical test that requires close monitoring on the quality with which the process is performed. The objective of this work is to show the results of the monitoring carried out during the past three years, of 5 quality indicators of blood cultures in the laboratory of the Hospital Clínico de la Pontificia Universidad Católica de Chile, considering pre-analytical, analytical and post-analytical aspects. In the 3 years monitored the mean contamination was 0,7%, 46% of adult bottles had adequate volume, match between Gram stain with final identification was 99.4%, 100% of correct participations were achieved in surveys of external quality control and Gram staining notification before 1 hour was 88.7%. With regard to proposed aims, in 2011 the laboratory complies with all, except the percentage of bottles with appropriate volume of blood inoculated. This indicator is very low and should be corrected as soon as possible since it is known that it is an important condition for optimum performance of blood cultures.

Analysis of the contribution of locally derived wastewater to the occurrence of Pharmaceuticals and Personal Care Products in Antarctic coastal waters.

Pharmaceuticals and Personal Care Products (PPCPs) are emerging pollutants detected in many locations of the world including Antarctica. The main objective of this review is to discuss the influence of the human population on the concentration, distribution and biological effects of PPCPs across the Antarctic coastal marine ecosystem. We carried out a review of the scientific articles published for PPCPs in Antarctic, supported by the information of the Antarctic stations reported by Council of Managers of National Antarctic Programs (CONMAP), Scientific Committee on Antarctic Research (SCAR) and Secretariat of the Antarctic Treaty (ATS). In addition, spatial data regarding the Antarctic continent was obtained from Quantarctica. Antarctic concentrations of PPCPs were more reflective of the treatment system used by research stations as opposed to the infrastructure built or the annual occupancy by station. The main problem is that most of the research stations lack tertiary treatment, resulting in elevated concentrations of PPCPs in effluents. Furthermore, the geographic distribution of Antarctic field stations in coastal areas allows for the release of PPCPs, directly into the sea, a practice that remains in compliance with the current Protocol. After their release, PPCPs can become incorporated into sea ice, which can then act as a chemical reservoir. In addition, there is no clarity on the effects on the local biota. Finally, we recommend regulating the entry and use of PPCPs in Antarctica given the difficulties of operating, and in some cases the complete absence of appropriate treatment systems. Further studies are needed on the fate, transport and biological effects of PPCPs on the Antarctic biota. It is recommended that research efforts be carried out in areas inhabited by humans to generate mitigation measures relative to potential adverse impacts. Tourism should be also considered in further studies due the temporal release of PPCPs.