Multicompartmental analysis of POPs and PAHs in Concepciόn Bay, central Chile: Part I - Levels and patterns after the 2010 tsunami.

Persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) were determined in abiotic samples from Concepción Bay in Central Chile. Samples were soxhlet extracted and injected in gas chromatography-mass spectrometry (GCMS). Polybrominated diphenyl ethers (PBDEs) showed the highest levels in air (3-1100 pg m-3), in water (2-64 pg L-1), in sediment, and soil (1-78 ng g-1 (dw)). PAHs were also high in the air (1-6 ng m-3), in water (1-7 ng L-1), in sediment (90-300 ng g-1 (dw)), and in soil (15-2300 ng g-1 (dw)). The polychlorinated biphenyls (PCBs) and chlorinated pesticides were generally low and did not show clear trends along the water column, with exception of PAHs. New data are presented in this work to assess the health status of a relevant coastal area in central Chile.

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.

Ecotoxicological sediment evaluations in marine aquaculture areas of Chile.

Given its geographic characteristics, the southern Chilean fjord area is subjected to growing environmental pressure from the development of diverse forms of aquaculture (i.e., fish, algae, shellfish). The sediments accumulate substances as a natural sink, and ecotoxicology assays offer a reliable and robust proxy for sediment quality analyses. This study's objective was to establish a mid-range toxicity base line for the sediments in the region by applying a battery of non-specific ecotoxicological assays. Sediment samples (28) were collected in the channels and fjords studied during the CIMAR-Fiordos 11 cruise (July 2005). The sediments were evaluated using different species endemic to the eastern Pacific as targets: Ampelisca araucana, Tisbe longicornis, Arbacia spatuligera, and Dunaliella tertiolecta. The conditions for each assay were reported previously. Of the four species used as ecotoxicological tools, only D. tertiolecta differed significantly from the control group (negative) in terms of its growth. This difference could be attributed to nutrient enrichment. In general, we concluded that, although local changes occurred in the sediments, the mesoscale magnitude of the ecotoxicological alterations was small. Nonetheless, a surveillance program should be implemented that would allow us to follow-up and analyze the changes that are taking place in the systems on broader scales of time and space.

Persistent Organic Pollutants (POPs) in the atmosphere of three Chilean cities using passive air samplers.

In this study passive air samplers containing polyurethane foam (PUF) disks were deployed in three cities across Chile; Santiago (STG) (n=5, sampling sites), Concepciόn (CON) (n=6) and Temuco (TEM) (n=6) from 2008 to 2009. Polychlorinated biphenyls (PCBs) (7 indicator congeners), chlorinated pesticides hexachlorocyclohexanes (HCHs), dichlorodiphenyl trichloroethanes (DDTs) and flame retardants such as polybrominated diphenyl ethers (PBDEs) were determined by gas chromatography coupled mass spectrometry (GC/MS). A sampling rate (R) typical of urban sites (4m3/day) was used to estimate the atmospheric concentrations of individual compounds. PCB concentrations in the air (pg/m3) ranged from ~1-10 (TEM), ~1-40 (STG) and 4-30 (CON). Higher molecular weight PCBs (PCB-153, -180) were detected at industrial sites (in Concepción). The HCHs showed a prevalence of γ-HCH across all sites, indicative of inputs from the use of lindane but a limited use of technical HCHs in Chile. DDTs were detected with a prevalence of p,p'-DDE accounting for ~50% of the total DDTs. PBDE concentrations in air (pg/m3) ranged from 1 to 55 (STG), 0.5 to 20 (CON) and from 0.4 to 10 (TEM), and were generally similar to those reported for many other urban areas globally. The pattern of PBDEs was different among the three cities; however, PBDE-209 was dominant at most of the sites. These results represent one of the few assessments of air concentrations of POPs across different urban areas within the same country. These data will support Chilean commitments as a signatory to the Stockholm Convention on POPs and for reporting as a member country of the Group of Latin America and Caribbean Countries (GRULAC) region.

EROD activity and biliary fluorescence in Schroederichthys chilensis (Guichenot 1848): biomarkers of PAH exposure in coastal environments of the South Pacific Ocean.

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.

Polybrominated Diphenyl Ethers (PBDEs) in Concepción Bay, central Chile after the 2010 Tsunami.

PBDEs (10 congeners) were analyzed using GC-MS in superficial sediments and organisms of the Concepción Bay after the 2010 Tsunami. From all congeners analyzed PBDE-47, -99, -100 and -209 were the most frequently detected. Concentrations (ngg(-1) d.w.) in sediments for ΣPBDE-47, -99, -100 were low (0.02-0.09). However, PBDE-209 showed significantly higher values ∼20ngg(-1) d.w. This result were ∼10 times lower than those reported in a previous study of the 2010 Tsunami. The high result might be influenced by the massive urban debris dragged by the 2010 Tsunami. In organisms, concentrations of PBDE-47, -99, -100 (∼0.4ngg(-1) d.w.) were higher than those found in sediments (∼0.04ngg(-1) d.w.). Differences in PBDE pattern were also observed between different levels of the trophic food chain (primary and secondary consumers). This is the first attempt to assess the current status of Concepción Bay after the 2010 Tsunami.

Levels of Persistent Organic Pollutants (POPs) in sediments from Lenga estuary, central Chile.

Superficial sediments from Lenga estuary in the VIII region of central Chile were analysed for Polychlorinated Biphenyls (PCBs) and Hexachlorobenzene (HCB). Organic carbon (OC) analysis was also performed and the statistical correlations (Pearson correlations) between compounds were also tested. Results showed the total PCB concentrations (ng g(-)(1)d.w.) fluctuated from ∼ 20 to 10,000. These levels are higher than those reported in other coastal sediments of the world. The PCB profile was dominated by middle to highly chlorinated congeners (6-Cl=40% and 7-Cl=30%). HCB concentrations (ng g(-)(1)d.w.), were lower than the PCBs and, fluctuated between 1 (at L1) and 870 (at L4). OC values ranged from 1% (L1) to 7% (L4) showing a significant positive correlations between OC% and PCBs (r=0.86; p<0.05) and for HCB (r=0.71). These results are an important contribution to knowledge of levels of POPs levels in coastal Chilean environments.

Integrated Use of Biomarkers (O : N Ratio and Acetylcholinesterase Inhibition) on Aulacomya ater (Molina, 1782) (Bivalvia: Mytilidae) as a Criteria for Effects of Organophosphate Pesticide Exposition.

The effect of residual concentrations of organophosphate pesticide chlorpyrifos (Lorsban 4E) on the activity of the acetylcholinesterase enzyme and oxygen : nitrogen ratio in the mussel Aulacomya ater was analyzed. Toxicity tests show a sensitivity to the pesticide in the bivalve estimated at 16 µg L(-1) (LC(50-96 hours)). Concentrations between 0.2 and 1.61 µg L(-1) were able to inhibit significantly the AChE activity, and concentrations between 0.8 and 1.61 µg L(-1) stimulate ammonia excretion and decrease oxygen : ammonia-N (O : N) ratio, with respect to the control group. A. ater proved to be a species sensitive to pesticide exposure and easy to handle in lab conditions. Thus, it is recommended as a bioindicator for use in programs of environmental alertness in the Eastern South Pacific coastal zone.

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Lenga Estuary, central Chile.

The Lenga Estuary is a small brackish wetland located southwest of San Vicente Bay, Region VIII, Chile. Surface sediment from nine sites in the estuary were analysed for PAHs and compared to Sediment Quality Guidelines (SQG). Sediment samples were freeze dried and soxhlet extracted for 16 h using DCM. Identification and quantification was carried out by HPLC. Organic carbon was also determined. Results showed total PAH concentrations ranged from 290 to 6118 (2025 ± 1975)ng g(-1) d.w. (2025 ± 1975). Results for organic carbon percentages ranged from 1% to 7%. Statistical analysis showed a significant positive correlation (Pearson test) between organic carbon percentage PAHs. Comparison of contaminant levels and international Sediment Quality Guidelines (SQG) (ERL and ER) suggested that sediment of the Lenga estuary did not show any ecotoxicological risk for benthic organisms where high levels of PAHs were detected. Monitoring of this and other contaminants is recommended in Chile.

Alteration of acetylcholinesterase activity in Semele solida (MOLLUSCA: SEMELIDAE) as a biochemical response to coastal anthropogenic impact.

Acetylcholinesterase (AChE) activity was analyzed as a molecular marker indicative of exposure to organophosphorus pesticide residues in individuals of the endemic clam species Semele solida in selected coastal locations of Chile's VIII Region. AChE activity was assayed in clams from (i) Penco Beach near the mouth of the Andalién River (Concepción Bay), (ii) Lenga Beach, near the mouth of the Lenga Estuary (San Vicente Bay), and (iii) Coliumo Beach, near the mouth of the Coliumo Estuary (Coliumo Bay). We also analyzed variations in protein content of clam hemolymph, and variability in the activity of AChE in relation to the sizes of the individual clams sampled. Collection of the clams was done using routine methods, during the spring of 2005, the period during which the use of pesticides is typically intensified in the surrounding forestry and agriculture. The results showed no significant correlation of AChE activity with either the size of the clam, or with the concentration of proteins in the hemolymph. The lowest AChE activity was observed in clams from mouth of the Andalién River (187.5 +/- 34.9 Umin(-1)) which was significantly less than that measured in specimens collected near the mouth of the Coliumo Estuary and the mouth of the Lenga Estuary. A very close relation was observed between the degree of anthropogenic inputs, ocean dynamics, and alterations in AChE activity in S. solida. This clam appears to be a useful indicator species, and AChE activity a sensitive marker for the presence of xenobiotics.

Trace metals in sediments of Southeast Pacific Fjords, north region (42.5 degrees to 46.5 degrees S).

Analyses of trace metals in benthic sediments from selected fjords and channels between 41 degrees 30' and 46 degrees 50'S, 75 degrees -72.3 degrees W were made after the CIMAR 1 Fjords expedition co-ordinated by CONA-Chile in 1995; the metals analyzed include Ba, Cd, Co, Cr, Cu, Ni, Pb, Sr, V and Zn. The objective of this study was to establish baseline values for these metals and to compare them with similar studies made in comparable, but geographically distinct, environments. Box core samples were collected at 35 stations and metal analysis was by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) using the MESS-2 reference standard. The ranked abundance by metal was Ba >> Sr >> V > Zn > Cr > Cu approximately Ni approximately Pb > Co >> Cd; these metals were not homogenous across the region and coefficients of variation were >10%. There were distinct groupings by metal and geographical area including the fjords, basins and channels. Depth profiles of the metal concentrations also varied spatially, e.g. Guafo, Laguna San Rafael, Moraleda, Corcovado, Quitralco, and Jacaf were predominantly homogeneous with depth profiles indicative of pristine systems experiencing few human impacts. In contrast, Aysen, Cupquelan and Puyuguapi Fjords had higher concentrations towards the surface, indicating elevated inputs in recent years. No major differences in metal content of the sediments were observed when compared with values from comparable natural systems in the northern hemisphere. Principal component analysis (PCA) grouped several seemingly isolated locations as having the same metal signature and indicated the pattern of dispersion across the region.

Assessment of EDTA in chromium (III-VI) toxicity on marine intertidal crab (Petrolisthes laevigatus).

Chromium poses a potential threat to coastal ecosystems. We used standard toxicity bioassays (semi-static, chronic) to evaluate EDTA as a chelating agent for reducing trivalent and hexavalent chromium toxicity on Petrolisthes laevigatus. Crab survival decreased linearly with increased chromium concentrations and dropped significantly beginning at 40 mg/L Cr (VI) and 80 mg/L Cr (III). No significant differences were observed with Cr (III) + EDTA as compared with untreated controls. Cr (VI) toxicity was greater than that of Cr (III), with low individual survival rates. The protective effect of EDTA in the medium increased crab survival by 41%-48%.

Evaluation of coastal waters receiving fish processing waste: Lota Bay as a case study.

Liquid wastes from the fish meal and oil processing industries produce serious environmental impacts in coastal embayments on the coasts of Chile and Peru. This article presents an analysis of an environmental monitoring program at Lota Bay, a shallow coastal indentation in central Chile (37 degrees S) exposed to industrial fishing activity. The study of the environmental impact produced by waste effluents permitted making an evaluation of the bay's capacity for seasonal recovery from this impact. Seasonal cruises were carried out during 1994 and in 1996, 1997, and 1998. Variables analyzed included salinity, temperature, dissolved oxygen, ammonium concentration and surface oil and grease. The hydrographic regime of Lota Bay follows a seasonal pattern, where, typical of most SE pacific embayments, waters from subsuperficial oxygen minimum zones moved into the bay. The percentages of dissolved oxygen were critical in the area of organic waste discharge. The impact of wastewater is related to the type and status of the fishery, including: (i) overloads of plant production lines, (ii) maintenance and cleaning of installations, and (iii) degree of shipboard fishing conservation. Major alterations were observed in summer, when the highest discharge of organic load occurred. In winter, an improvement in the re-aeration conditions reduced the impact. Remedial measures implemented beginning in 1997 arose from the monitoring program and had to be separated into two recovery factors including (a) internal management of plants and (b) treatment of plant effluents.

Dissolved oxygen content as an index of water quality in San Vicente Bay, Chile (36 degrees 45'S).

The present report describes some effects of industrial and municipal effluents on the waters of San Vicente Bay. Analyses of the main substances contained in the fishing industry effluent suggest rating criteria based on the oxygen saturation of the water as an assessment of organic pollution. Six cruises were carried out throughout the Bay, from June to December 1996. Water samples were analyzed for dissolved oxygen, oil and grease content, and sediment samples for organic matter content. Water parameters (salinity, temperature) were used to characterize the Bay's hydrography, and to calculate values for oxygen saturation. The measurements demonstrated a local broad range of oxygen deficit, with a maximum of 45% in the winter to 95% in the spring. In November more than 65% of the Bay's area showed oxygen deficits greater than 40%. Organic matter was unusually high in sediments along the northern sector of the Bay. The results suggest that the oxygen depletion was a representative parameter for establishing a relative scale of water quality in this Bay.