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.

Single and Combined Effects of Cypermethrin and UVR Pre-Exposure in the Microalgae Phaeodactylum Tricornutum.

Coastal marine microalgae are exposed to anthropogenic pollutants, including pesticides from aquaculture/agriculture/household uses. Some microalgae species, such as Phaeodactylum tricornutum, can induce and accumulate UV-absorbing compounds (UACs) upon ultraviolet radiation (UVR) exposure to prevent deleterious effects. Tolerance mechanisms activated by natural stressors might also protect organisms from anthropogenic stressors. This work assesses the effects of the insecticide cypermethrin (Cyp) and UVR in the marine microalgae P tricornutum. Considering the pro-oxidant properties of both stressors and UACs' induction in P tricornutum, lethal and sublethal effects of Cyp were tested in cultures with and without UVR acclimation. After a 24-h exposure to 10 µg L-1 of technical Cyp or culture medium, UACs, growth, glutathione-S-transferase activity (GST), sulfhydryl groups (SH-g), and lipid peroxidation (LPO) were analyzed. Results showed differences in terms of growth between Cyp and Cyp + UVR pre-exposure. UACs' content was induced after UVR acclimation and diminished after 24 h of growth in control and UVR pre-treated cultures, while levels remained constant under Cyp exposure. A single Cyp exposure exerted GST induction, SH-g depletion, and LPO increments. In UVR-acclimatized treatments, oxidative stress responses showed similar or more pronounced effects than the single chemical exposure, suggesting a potential additive effect of the UVR acclimation. The contrasting effects of Cyp + UVR observed between growth and biochemical responses suggest different compensatory mechanisms that need to be further investigated. Also, it highlights the need to include both lethal and sublethal endpoints to understand microalgae's tolerance and its significance in the multiple stressors' context.

Spatial distribution patterns and identification of microplastics on intertidal sediments from urban and semi-natural SW Atlantic estuaries.

Although estuaries act as a sink of many pollutants, the assessment of microplastics pollution in these transition environments remain scarce or unknown. Sediments from estuarine intertidal areas possess a great ecological concern but also could act as a sink of both buoyant and non-buoyant plastic debris. In this work, we have compared microplastic abundances and their main characteristics (size, shape, colour and polymer type) on intertidal sediments from SW Atlantic Argentinean estuaries (Samborombón, Mar Chiquita, Quequén Grande and Bahía Blanca). The mean microplastics abundance in surface sediments among estuaries was ranged from 0 to 1030 ± 657 items per kg d. w. Upper intertidal areas have shown significant higher microplastic abundances in comparison with lower intertidal zones (p < 0.05). In general, higher mean abundances were observed in surface (0-10 cm) compared to deeper sediments (10-30 cm), which revealed recent deposition trends of microplastics particles. However, higher microplastic abundances were observed in deeper sediments from Bahía Blanca (p < 0.05). Large (MPs, 1-5 mm) and small microplastics (MMPs, 1-0.1 mm) were observed in sediments from all estuaries, representing from 17 to 100% of total microplastics abundance. In terms of shape, fragments and films forms were dominant in all samples while fibers and foams were moderately or poorly represented. White, black, blue and transparent particles were observed as the main colour contribution of microplastics in sediments. The most common polymers identified included polyethylene, polyethylene terephthalate/polyester, polyvinyl chloride and polypropylene. The results showed that microplastic characteristics are different among the estuarine environments, which suggests different anthropogenic sources. Besides, deeper sediments should also be included on intertidal sediment monitoring to identify potential environmental liabilities from anthropogenically impacted estuaries.

Methylmercury biomagnification in coastal aquatic food webs from western Patagonia and western Antarctic Peninsula.

Mercury (Hg) is a global pollutant of concern because its organic and more toxic form, methylHg (MeHg), bioaccumulates and biomagnifies through aquatic food webs to levels that affect the health of fish and fish consumers, including humans. Although much is known about trophic transfer of MeHg in aquatic food webs at temperate latitudes in the northern hemisphere, it is unclear whether its fate is similar in biota from coastal zones of the southeastern Pacific. To assess this gap, MeHg, total Hg and food web structure (using δ13C and δ15N) were measured in marine macroinvertebrates, fishes, birds, and mammals from Patagonian fjords and the Antarctic Peninsula. Trophic magnification slopes (TMS; log MeHg versus δ15N) for coastal food webs of Patagonia were high when compared with studies in the northern hemisphere, and significantly higher near freshwater inputs as compared to offshore sites (0.244 vs 0.192). Similarly, in Antarctica, the site closer to glacial inputs had a significantly higher TMS than the one in the Southern Shetland Islands (0.132 vs 0.073). Composition of the food web also had an influence, as the TMS increased when mammals and seabirds were excluded (0.132-0.221) at a coastal site. This study found that both the composition of the food web and the proximity to freshwater outflows are key factors influencing the TMS for MeHg in Patagonian and Antarctic food webs.

Estrogenicity and intersex in juvenile rainbow trout (Oncorhynchus mykiss) exposed to Pine/Eucalyptus pulp and paper production effluent in Chile.

Pulp and paper mill effluents (PPMEs) have been shown to increase gonad size, cause early maturation, and disrupt hormone functions in native and non-native Chilean fish. In this study, we assessed reproductive (plasma vitellogenin; VTG, gonad development) and metabolic (ethoxyresorufin-O-deethylase activity; EROD) end points, relative liver size (LSI) and condition factor (K) of juvenile female and male rainbow trout exposed to effluents. Unlike previous studies, which have focus either on the specific effects of effluent on fish in laboratory exposures or biotic population statuses downstream of discharge sites, we simultaneously assessed the impacts of PPMES on trout using two approaches: (1) laboratory exposures of tertiary treated PPME produced from processing Eucalyptus globulus or Pinus radiata; and (2) in situ bioassay downstream of the combined discharge of the same pulp mill. Despite an increase in the average gonadosomatic index (GSI) in exposed fish, no statistical differences in gonad size between exposed and unexposed individuals was detected. However, both female and male fish exposed to effluents showed significantly higher concentrations of plasma VTG, so more in fish exposed to Eucalyptus-based effluent when compared to Pinus PPME. In addition, male fish showed intersex characteristics in all exposure assays (Eucaliptus and Pinus) and, despite the low concentration of effluent in the river (<1% [v/v]), similar responses were observed in the caged fish. Finally, EROD activity was induced in both in situ exposures and laboratory assays at the higher PPME concentration (60-85% PPME). This study confirms estrogenic effects in Chilean fish exposed to PPME and the necessity for biological effects monitoring in addition to the assessment of physical-chemical endpoints as required in current government regulations.

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.

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.

Seasonal mercury concentrations and δ15N and δ13C values of benthic macroinvertebrates and sediments from a historically polluted estuary in south central Chile.

The Lenga Estuary is one of the most industrialized sites in south central Chile where the historic operation of chlor-alkali plants resulted in large quantities of mercury (Hg) being deposited into the estuary. This historical contamination may still represent a risk to the biota in the estuary. To investigate this four macroinvertebrates, Neotrypaea uncinata (ghostshrimp), Elminius kingii (barnacle), Hemigrapsus crenulatus (shore crab) and Perinereis gualpensis (ragworm) were collected seasonally from three different sites in the Lenga Estuary and one in a reference estuary (Tubul Estuary), and analyzed for Hg and stable isotopes (δ(15)N and δ(13)C). Mercury concentrations in Lenga sediments ranged from 0.4 ± 0.1 to 13 ± 3 mg/kg, while those in Tubul sediments ranged from 0.02 ± 0.01 to 0.07 ± 0.09 mg/kg. Total Hg concentrations of invertebrates were significantly different between estuaries (p<0.05), but not by species or season for each estuary (p>0.05). In contrast, organic Hg concentrations were different by species and season with shore crab muscle tissues exhibiting the greatest percent difference. Site-specific relationships demonstrated that total Hg concentrations in ragworm best reflected the total Hg sediment mercury concentrations. Signatures of δ(13)C were correlated to the organic Hg % rather than total Hg. This suggests that organic Hg concentrations in these species were related to the carbon sources.

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.

Divalent metal (Ca, Cd, Mn, Zn) uptake and interactions in the aquatic insect Hydropsyche sparna.

Despite their ecological importance and prevalent use as ecological indicators, the trace element physiology of aquatic insects remains poorly studied. Understanding divalent metal transport processes at the water-insect interface is important because these metals may be essential (e.g. Ca), essential and potentially toxic (e.g. Zn) or non-essential and toxic (e.g. Cd). We measured accumulation kinetics of Zn and Cd across dissolved concentrations ranging 4 orders of magnitude and examined interactions with Ca and Mn in the caddisfly Hydropsyche sparna. Here, we provide evidence for at least two transport systems for both Zn and Cd, the first of which operates at concentrations below 0.8 µmol l(-1) (and is fully saturable for Zn). We observed no signs of saturation of a second lower affinity transport system at concentrations up to 8.9 µmol l(-1) Cd and 15.3 µmol l(-1) Zn. In competition studies at 0.6 µmol l(-1) Zn and Cd, the presence of Cd slowed Zn accumulation by 35% while Cd was unaffected by Zn. At extreme concentrations (listed above), Cd accumulation was unaffected by the presence of Zn whereas Zn accumulation rates were reduced by 58%. Increasing Ca from 31.1 µmol l(-1) to 1.35 mmol l(-1) resulted in only modest decreases in Cd and Zn uptake. Mn decreased adsorption of Cd and Zn to the integument but not internalization. The L-type Ca(2+) channel blockers verapamil and nifedipine and the plasma membrane Ca(2+)-ATPase inhibitor carboxyeosin had no influence on Ca, Cd or Zn accumulation rates, while Ruthenium Red, a Ca(2+)-ATPase inhibitor, significantly decreased the accumulation of all three in a concentration-dependent manner.

Multibiomarker approach at different organization levels in the estuarine Perinereis gualpensis (Polychaeta; Nereididae) under chronic and acute pollution conditions.

This work aimed to study biochemical biomarkers and population responses in the polychaete Perinereis gualpensis (Nereididae) from two Chilean estuaries, Lenga (36°45'S; 73°10'W) and Tubul-Raqui (37°14'S,73°26'W). Lenga estuary is characterized by high mercury and PAH levels as consequence of several historic incidental spills while Tubul is mainly impacted by intensive fish activity. Raqui estuary, with low anthropogenic impact was considered the reference site. Worms were collected in winter and summer periods and tissues were differentiated between anterior (first 40 segments) and posterior region (the rest of the body). Levels of the antioxidant glutathione (GSH), glutathione-S-transferase (GST) activity, total antioxidant capacity against peroxyl radicals (ACAP), lipid peroxidation (TBARS) levels, Na+, K+-ATPase activity (NKA) and metalothioneins (MTs) content were determined in each region. L3 (combined length of prostomiun+peristomiun+first segment) length, size, frequency, histograms and density of individuals were studied in all sites and seasons. Significant differences (p<0.05) were observed among sites for most of the biochemical responses (GSH, GCL, GST, ACAP and TBARS), showing variation between seasons and body regions. Population responses in the most polluted estuary (Lenga) showed differences in size, frequency, lengths and low densities compared with lower impacted sites, indicating the costs associated with tolerance in organisms chronically exposed to estuarine pollution.