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.

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.

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.

Distribution of PAHs and trace elements in Spartina densiflora and associated sediments from low to highly contaminated South American estuarine saltmarshes.

Estuarine saltmarshes from South America are exposed to several anthropogenic impacts due to diverse human activities that occur in both Atlantic/Pacific coastal environments. Primarily, chemical and petrochemical industries negatively impact saltmarshes generating inputs/deposition of non-essential trace elements (NTEs) and polycyclic aromatic hydrocarbons (PAHs) in sediments. The native cordgrass Spartina densiflora inhabits a wide range of environments, from non-impacted to highly impacted areas. It is important to know its performance towards pollution in different environmental settings in South America. The content of Cd, Hg, Pb, and PAHs was determined in the roots and leaves of S. densiflora, bulk sediments (Bs), and rhizosediments (Rs) of estuaries from Argentina, Brazil, and Chile. Differences in NTEs and PAHs levels were observed between Bs, Rs, and Spartina tissues from different saltmarsh areas. Differences in Rs/Bs (RHICF; rhizosediments concentration factors), roots/Bs (RCF; roots concentration factors) and leaves/roots (TF; translocation factors) factors were also found. In terms of NTEs, S. densiflora showed a high capability to increase levels in their Rs (RHICF>1) and bioconcentrate Cd in roots (RCF > 1), while no general translocation (TF < 1) was observed. Conversely, in cordgrass tissues, Bs and Rs, PAHs contents showed RCF and TF > 1, which was in line with lower levels in Rs related to Bs (RHICF<1) in most sites. These findings showed the S. densiflora capacity to retain, remove and/or translocate priority contaminants depending on intrinsic chemical characteristics and the level of contamination. The present study enables future considerations regarding the biomonitoring and phytoremediation/stabilization capabilities of Spartina in coastal environments.

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.

Sex-Related Embryotoxicity of Pulp Mill Effluent Extracts in Medaka (Oryzias latipes) Female Leucophore-free FLFII Strain.

The aim of the present study was to evaluate the effects of exposure to Chilean pulp mill effluent extracts on developing postfertilized medaka embryos before and after sex definition relative to sex steroids (testosterone and 17beta-estradiol) and a wood phytoestrogen (beta-sitosterol). Our study included 2 waterborne semichronic exposure experiments, using a 24-h post fertilization (hpf) unknown-sex FLFII (female leucophore free) group and a second 72-hpf FLFII phenotypic sex-identified group (male autofluorescence leucophore) strain of medaka embryos. Chronic exposure of both FLFII strain embryo groups showed similar delay in time to hatch and decreased hatchability. Teratogenic responses such as vertebral malformation (fusion, incomplete formation, and lack of vertebral formation process) and pericardial edema were observed in both experiments, with a high percentage related to FLFII fluorescent leucophore-identified males. In addition, high mortality associated with severe malformations was observed in male and female embryos exposed to testosterone. Our research has demonstrated that exposure to Chilean mill effluent extracts caused severe male medaka embryotoxicity (in postfertilized embryos) before and after sex definition and, irrespective of the experimental group and effluent treatment, suggests partial removal following secondary treatment. Furthermore, differences in the severity and type of teratogenic effects with previous experiments (d-rR medaka strain), are associated with the unique phenotypes of this medaka mutant strain. Environ Toxicol Chem 2021;40:2297-2305. © 2021 SETAC.

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.

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.

Spatial and temporal distribution of Persistent Organic Pollutants and current use pesticides in the atmosphere of Argentinean Patagonia.

XAD-based passive air samplers (PAS) were used to evaluate organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and some current use pesticides (chlorotalonil, trifluralin and dichlofluanid) in the atmosphere of Argentinian Patagonia. The PAS were deployed for 12 months during three consecutive years along a longitudinal (Rio Negro watershed) and a latitudinal (Patagonian coast) transect. Endosulfan, trifluralin and DDT-related substances were the most prevalent pesticides in the Rio Negro watershed, an intensive agricultural basin, consistent with ongoing use of endosulfan at the time of sampling. Concentrations of industrial contaminants were low (mean 25 pg/m3 and 1.9 pg/m3 for Σ38 PCBs, and Σ5PBDEs, respectively) and similar among sites. However, along the Patagonian coast, air concentrations of total contaminants were highly variable (14-400 pg/m3) with highest values recorded at Bahia Blanca, an important industrial area that is also downwind of the most intensively agriculturally used area of Argentina. Contaminant levels decreased toward the south, with the exception of the southernmost sampling site (Rio Gallegos) where a slight increase of total pollutant levels was observed, mainly due to the lower chlorinated PCB congeners. Interannual variability was small, although the last year tended to have slightly higher levels for different contaminant groups at most sampling sites. This large-scale spatial atmospheric monitoring of POPs and some CUPs in the South of Argentina highlights the important and continuing role of rural and urban areas as emission sources of these chemicals.

Biotransport of persistent organic pollutants in the southern Hemisphere by invasive Chinook salmon (Oncorhynchus tshawytscha) in the rivers of northern Chilean Patagonia, a UNESCO biosphere reserve.

Biotransport is often associated with migration patterns of species, including large, anadromous salmonids. Several studies have reported biotransport of persistent organic pollutants in the Northern Hemisphere, but there is no published information on biotransport ocurring south of the equator. Chile's Patagonia is one of the last largely intact natural areas in the world. The objective of this study was to determine whether persistent organic pollutants are transported by the invasive Pacific Chinook salmon (O. tshawytscha) from the Pacific Ocean to Chilean Patagonia. Samples of juvenile and adult Chinook salmon were analyzed for polychlorinated biphenyls, pesticides and polybrominated diphenyl ethers. The results revealed that concentrations of POPs in adults migrating into Patagonian rivers were significantly higher than those found in juveniles migrating seaward. A mass balance analysis indicates that Chinook salmon are a source of persistent organic pollutants to Chilean Patagonia inland waters. Capsule: Biotransport of Persistent Organic Pollutants (POPs) by Chinook salmon (O. tshawytscha) from the Pacific Ocean to Chilean Patagonia has been confirmed by mass balance of POPs.

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.

Accumulation and potential sources of lead in marine organisms from coastal ecosystems of the Chilean Patagonia and Antarctic Peninsula area.

Environmental concentrations of Pb have been increased due to anthropogenic activities, which have provoked the released of this element to the environment in large amounts. To understand how Pb behaves in remote southern marine ecosystems, we measured Pb concentrations and isotope ratios in biota from coastal marine ecosystems of the Chilean Patagonia and the Antarctic Peninsula area. Lead concentrations in the aquatic organisms ranged from 0.02 to 1.19 mg kg-1 d.w. In Patagonia, higher Pb levels were found in fish than in invertebrates (crab, shrimp, porifera, limpet and shellfish). In comparison with the baseline reference values from other parts of the world, fishes exhibited lower Pb levels. The results of Pb isotopic compositions indicated that the bioaccumulation of Pb in marine organisms come from different anthropogenic sources. These Pb levels might be useful for further studies that allow a deeper evaluation of sources for Pb contamination in these remote ecosystems.

Legacy and current-use pesticides (CUPs) in the atmosphere of a rural area in central Chile, using passive air samplers.

Polyurethane foam (PUF) disks in passive air samplers (PAS) and passive dry deposition (Pas-DD) collectors were used to assess the presence of persistent organic pollutants (POPs) and current-use pesticides (CUPs) in a rural area of central Chile (Peumo, VI Region). The samplers were exposed from September 2015 (spring) to March 2016 (summer), with the PUFs collected at intervals of 30, 60, and 90 days. Both samplers (PUF-PAS and Pas-DD) captured more than one pesticide per sampling period. Chlorpyrifos-ethyl and pyrimethanil presented the highest air concentration with PUF-PAS (3470.2 ng m-3 for chlorpyrifos-ethyl and 52.8 ng m-3 for pyrimethanil). The deposited amount of chlorpyrifos-ethyl, pyrimethanil, penconazole, diazinon and malathion in some Pas-DD, was superior to amount of pesticides captured by PUF-PAS. Differences between the amount deposited and captured by each sampler should be studied in greater detail, because wind speed, atmospheric particulate matter size and sampler design are some fundamental variables in this process. These results provide preliminary information on the presence of current-use pesticides in the atmosphere of Peumo, VI Region, serving as a foundation for future environmental monitoring programs.

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.

Trophic transfer of cadmium in marine food webs from Western Chilean Patagonia and Antarctica.

In aquatic environments, Cd contamination is a great concern because this non-essential metal presents risks both for wildlife and human health. Data about the concentration and transfer of Cd in Patagonian and Antarctic aquatic food webs are crucial for assessing the impacts of this element in pristine ecosystems. Consequently, the concentration of Cd was measured in thirty-two species collected in the 2014 austral summer from two locations of the Western Patagonia and two locations of the Antarctic Peninsula. The main objective of this work was to assess the relationship between Cd concentration and trophic level determined by δ15N. In the studied trophic positions, Cd showed a positive relationship between concentration and trophic level, which suggests biomagnification of this element in macroinvertebrates. However, there was a significant dilution when higher trophic organisms were considered.