Essential and toxic elements in juvenile migratory commercial fish species in the Paraná River alluvial valley (South America): an approach for aquatic environmental monitoring.

The Paraná River is the sixth largest in the world, and the lower section of the river is one of the largest and most productive floodplain wetlands in South America. The alluvial plain is an important habitat for nursery and feeding areas for commercial fish; however, it has been heavily anthropized due to industries, agricultural activities, and the growth and expansion of metropolitan areas. The aim of this study was to determine element accumulation (As, Cd, Cr, Cu, Fe, Mn, Pb, and Zn) in young-of-the-year fish muscle from a floodplain lagoon of the lower Paraná River (Argentina) during summer and winter seasons, in relation with abiotic matrices (water and sediment). Four commercial fish species were assessed: sábalo (Prochilodus lineatus), boga (Megaleporinus obtusidens), dorado (Salminus brasiliensis), and pirapitá (Brycon orbignyanus). The concentrations of eight elements were detected by quadrupole inductively coupled plasma mass spectrometry. In water samples, Cd, Cr, Mn, Fe, and Zn levels were under the permissible limits for aquatic biota protection in both seasons, except for Pb (> 1 µg L-1) and Cu (> 2 µg L-1). In sediment, the average concentrations of all elements were under the limits set by national and international regulatory authorities. Differences in elemental concentrations between species and seasons were found. In general, the levels of elements in water were higher in summer than in winter, while in sediment, the lowest concentrations of elements were detected during the summer. The order of element concentration in fish muscle was Cd (0.01-0.04 µg g-1) < As (0.02-0.16 µg g-1) < Pb (0.03-0.23 µg g-1) < Mn (0.77-4.32 µg g-1) < Cu (1.01-4.07 µg g-1) < Cr (1.09-4.30 µg g-1) < Zn (15.8-31.7 µg g -1) < Fe (12.6-49.7 µg g-1). The accumulation assessment showed that the four fish species significantly accumulate Cr, Cu and Zn, and As and Zn from water and sediment, respectively. The correlation analysis showed a relationship between fish size and As, Cr, Cu, Fe, Mn, and Zn concentrations. Similarly, the highest values of element concentrations in muscle were detected during the summer when the fishes are early juveniles. The level of As, Cd, and Pb detected in B. orbignyanus, M. obtusidens, and P. lineatus juveniles suggested that these species had the potential to be used as biomarkers for assessing accumulation of toxic elements in the environment. Also, this study reveals that the accumulation patterns differ between size and fish species, which should be a considered insight at the moment of selecting a bioindicator to monitor pollution in the ecosystem.

Essential and non-essential elements in marine silverside Odontesthes argentinensis from southwestern Atlantic coast: Tissues bioaccumulation, biomagnification and public health risk assessment.

In order to assess the metal pollution in the southwestern Atlantic coast, levels of eleven metals: Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, and Zn and one metalloid: As in water and tissues of Odontesthes argentinensis from the Samborombón Bay (SB) and Partido de La Costa (PC) were examined. Additionally, bioconcentration, and bioaccumulation factors, estimated daily intake (EDI) for adults and children, and the hazard risk for fishermen and general populations were evaluated. Cadmium, Cu and Zn levels in the water samples exceeded the limits established by international guidelines for the protection of aquatic life in marine environments (CCME). The liver showed the highest concentrations of As, Cu, Fe, and Zn, while muscle showed the least levels of all elements examined. Bioaccumulation of Cd, Cu, Mn, Pb and Zn were observed in all tissues, while Ba and Sr bioaccumulated significantly in the gills. The fish δ15N values significantly varied between sites, however, no biodilution or biomagnification was observed. The Target Hazard Quotients (THQ) and the Carcinogenic Risk (CR) indices suggest that there is no human health risk to the fishermen and general populations from the O. argentinensis consumption. Furthermore, As (27%) and Cr (33%) concentrations in silversides from PC and SB, respectively, exceeded the levels recommended by local and international guidelines.

Health risk assessment and differential distribution of Arsenic and metals in organs of Urophycis brasiliensis a commercial fish from Southwestern Atlantic coast.

The concentrations of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, and Zn were analyzed in muscle, gills, and liver of Urophycis brasiliensis from two Southwestern Atlantic catch areas (Brazil and Argentina). Additionally, the health risk of general and fishermen populations through fish consumption was estimated. The gills showed the highest concentrations of most of the elements, followed by the liver. With the exception of As, the muscle was the organ with the lowest concentrations of most elements. Levels of arsenic in muscle of U. brasiliensis were exceeded the maximum permissible levels for human consumption recommended by local and international guidelines. The target hazard quotients (THQs) and the carcinogenic risk (CR) showed no risk for individual and all elements. These results highlight the importance of arsenic speciation in U. brasiliensis muscle in order to generate more reliable risk estimates.

Atrazine pollution in groundwater and raw bovine milk: Water quality, bioaccumulation and human risk assessment.

Atrazine herbicide can bioaccumulate over time and thus affect humans for generations to come. However, scarce studies have evaluated its bioaccumulation potential in bovine milk, a nutritional staple for children and the elderly both domestically and internationally. This study aimed to determine its concentration in groundwater and bovine milk, as well as the risks it is likely to pose for human health. Eighteen dairy farms in the Pampean plain of Argentina were analyzed. A strong correlation was found between the chemical composition and the geomorphological characteristics of the plain. In addition, increased salinity was observed in the groundwater at greater distances from the aquifer's recharge area. Atrazine was quantified in 50 % of the groundwater samples (at values ranging from 0.07 to 1.40 µg/L), and in 89 % of the bovine milk samples (from 2.51 to 20.97 µg/L). Moreover, atrazine levels in 44.4 % of the groundwater samples and 11.1 % of the bovine milk samples (n = 18) exceeded the limits internationally established as safe for human consumption. The hazard quotient (HQ) values of the compound were negligible for children and adults, both in groundwater (child = 9.7E-4, adult = 4.5E-4) and in milk (child = 1.0E-2, adult = 1.6E-3). The estimated cancer risk (CR) values need further evaluation (child = 7.8E-6, adult = 3.6E-6 in groundwater; child = 6.6E-5, adult = 1.3E-5 in milk). In both types of samples, the HQ and CR of residual atrazine were higher for children than for adults. Nevertheless, bioaccumulation factors suggest that dairy cows have a moderate capacity to incorporate atrazine from abiotic matrices. This is the first report on residual atrazine in bovine milk in Argentina. The results presented here indicate that the status of atrazine contamination in the area should continue to be monitored in order to assess its long-term impact on public health.

Distribution and Accumulation of Trace Elements in Organs of Juvenile Fishes from a Freshwater System (Paraná River, South America).

The concentrations of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn (TE) in four juvenile fishes (Acestrorhynchus pantaneiro, Salminus brasiliensis, Brycon orbignyanus, and Megaleporinus obtusidens) and associated sediment water from the Lower Paraná River were measured. For muscle, gills, and liver fishes, the TE accumulation in the muscle, gills, and liver was evaluated. The TE concentration was measured by quadrupolar inductively coupled plasma mass spectrometry (Q-ICP-MS). Cadmium (0.25 ± 0.07 µg L-1), Cu (3.00 ± 1.44 µg L-1), Fe (612 ± 69 µg L-1), and Pb (1.92 ± 1.20 µg L-1) in water and As (4.1-6.9 µg g-1), Cr (20.1-31.4 µg g-1), Cu (10.7-19.2 µg g-1), Mn (351.3-482.2 µg g-1), and Ni (24.5 ± 10.9 µg g-1) in sediments exceeded the guide values for the conservation of aquatic life. In general, muscle of omnivorous species (B. orbignyanus and M. obtusidens) showed higher values of elements than those of carnivorous species (A. pantaneiro and S. brasiliensis). However, TE concentrations varied with fish species and organs. Independently of the examined species, the highest concentrations of Cr and Pb were in the muscle and gills, respectively. Cadmium, Cu, and Fe concentrations were higher in the liver than in gills and muscle in all four fish species. These results were consistent with the tissue selectivity index analyzed. For the four species, major essential elements showed the highest accumulation. However, the accumulation of toxic elements in omnivorous fish was higher than in carnivorous fish. The individual pollution load index indicated that sediment was very polluted with As and Pb, but based on the combined ecological indexes, low elemental sediment pollution in the Espinillo Lake was revealed.

Bioaccumulation of 10 trace elements in juvenile fishes of the Lower Paraná River, Argentina: implications associated with essential fish growing habitat.

This study assessed the concentration, bioconcentration, and bioaccumulation of As, Cd, Co, Cr, Cu, Mg, Mn, Ni, Pb, and Zn in juvenile fishes (Acestrorynchus pantaneiro, Brycon orbygnianus, Cyphocharax voga, Megaleporinus obtusidens, Odontesthes bonariensis, Pimelodus maculatus, Prochilodus lineatus, Salminus brasiliensis, and Schizodon borelli) in the Lower Paraná River (Argentina), the most extensive floodplain from the Plata Basin. The floodplain is crucial for the reproduction and growth of various species such as P. lineatus, M. obtusidens, and S. brasiliensis, which complete their life cycle in this environment. In total, 90 individuals were sampled for nitrogen stable isotope, and trace element analysis in muscle tissue, water, and sediment was analyzed. The results show that all the studied species bioaccumulate Cr, Mg, Ni, and Zn. In particular, B. orbygnianus and P. maculatus presented the highest bioaccumulation factor for Cr. A biodilution of Co through the food chain was observed. No positive correlation was found between element concentration and trophic level, but we observed significant differences between trophic guilds (herbivorous, omnivorous, and carnivorous). Our findings suggest that feeding habits determine trace element concentrations. To establish differential behavior between different species within the aquatic web further studies are necessary, particularly in the floodplain of the Paraná, which is a crucial nursery area for most commercially important fishes from the Plata Basin. Graphical abstract.

Identification of nurseries areas of juvenile Prochilodus lineatus (Valenciennes, 1836) (Characiformes: Prochilodontidae) by scale and otolith morphometry and microchemistry

The streaked prochilod Prochilodus lineatus (Valenciennes) is a commercially freshwater species from South America, distributed in the Plata basin. In the present work the morphometry (circularity, rectangularity, form factor, OL/OW and ellipticity indices) and chemistry (Sr:Ca, Ba:Ca, Zn:Ca) of lapilli otolith, and geometric morphometry of scales of streaked prochilod juveniles, in two sites in the Plata basin (Uruguay River and Estrella Wetland), were compared to determine if they are area-specific and to identify possible breeding areas. Otolith Ba:Ca ratios was 0.017±0.003 mmol/mol for Uruguay River while for Estrella Wetland individuals was bellow the detection limits. Zn:Ca ratios tended to be higher for the latter (0.03±0.002 mmol/mol). Significantly high circularity and low rectangularity values were obtained for Estrella Wetland otoliths (p < 0.05), while no significant differences for form factor, OL/OW and ellipticity were observed between sampling sites. Considering all scale geometric morphometry variables, discriminant analysis showed a good percentage of classification of individuals (90.5% for Estrella Wetland and 85.7 % for Uruguay River). These results indicate that the otolith microchemisty and morphometry (circularity and rectangularity indices) and scale morphometry are good markers of habitat and represent a potential tool for identification of streaked prochilod nursery areas.(AU)

El sábalo Prochilodus lineatus (Valenciennes) es una especie de importancia comercial de agua dulce de Sudamérica, distribuida en la cuenca del Plata. En este trabajo se comparó la morfometría (índices de circularidad, rectangularidad, factor de forma, OL/OW y elipticidad) y microquímica (Sr:Ca, Ba:Ca y Zn:Ca) del otolito lapilli, y la morfometría geométrica de las escamas de sábalos juveniles capturados en dos sitios de la cuenca del Plata (Río Uruguay y bañado la Estrella), para determinar si existen diferencias área-especificas e identificar posibles sitios de cría. La relación Ba:Ca del otolito fue 0.017±0.003 mmol/mol para el río Uruguay mientras que estuvo por debajo del límite de detección para los individuos del bañado la Estrella. La relación Zn:Ca tendió a ser más alta en el bañado la Estrella (0.03±0.002 mmol/mol). Se obtuvieron valores significativamente altos de circularidad y bajos de rectangularidad para el bañado la Estrella (p < 0.05), mientras que no se hallaron diferencias para el factor de forma, OL/OW y elipticidad. Considerando la morfometría geométrica de las escamas, el análisis discriminante mostró buenos porcentajes de clasificación (90.5% para el bañado la Estrella y 85.7 % para el Río Uruguay). Estos resultados indican que la microquímica y morfometría del otolito (índices de rectangularidad y circularidad) y la morfometría de las escamas son buenos marcadores de hábitat y representan una herramienta potencial para la identificación de sitios de cría del sábalo.(AU)