Seasonal arsenic in catfish (Siluriformes, Ariidae) and the hydrochemical conditions of two areas in a Ramsar site on the Brazilian coast.

The construction of a data bank concerning metal and metalloid content of bioindicator fish from coastal areas is very important as it can help environmental managers in decision making. In natural conditions, the concentration of elements can be influenced by abiotic parameters such as water salinity. In this study, catfish Cathorops spixii were evaluated concerning the total arsenic (As) concentration in the muscle tissues of individuals subjected to different abiotic conditions in the Cananéia-Iguape Estuarine-Lagoon Complex (CIELC), which was recently included on the Ramsar list of wetlands of international importance. Seventy-four catfish were seasonally caught in the northern and southern regions of the CIELC and their hydrochemical parameters were obtained. C. spixii from the southern, best preserved, area showed arsenic concentrations around ten times higher than the maximum limit established for fish intended for human consumption. However, these high concentrations of arsenic could be associated with the abiotic parameters of the water, such as salinity variations, in this area.

Microscale Toxicity Identification Evaluation (TIE) for interstitial water of estuarine sediments affected by multiple sources of pollution.

Estuaries in the world are affected by different contamination sources related to urbanisation and port/industrial activities. Identifying the substances responsible for the environmental toxicity in estuaries is challenging due to the multitude of stressors, both natural and anthropogenic. The Toxicity Identification and Evaluation (TIE) is a suitable way of determining causes of toxicity of sediments, but it poses difficulties since its application is labour intensive and time consuming. The aim of this study is to evaluate the diagnosis provided by a TIE based on microscale embryotoxicity tests with interstitial water (IW) to identify toxicants in estuarine sediments affected by multiple stressors. TIE showed toxicity due to different combinations of metals, apolar organic compounds, ammonia and sulphides, depending on the contamination source closest to the sampling station. The microscale TIE was able to discern different toxicants on sites subject to different contamination sources. There is good agreement between the results indicated in the TIE and the chemical analyses in whole sediment, although there are some disagreements, either due to the sensitivity of the test used, or due to the particularities of the use of interstitial water to assess the sediment toxicity. The improvement of TIE methods focused on identifying toxicants in multiple-stressed estuarine areas are crucial to discern contamination sources and subsidise management strategies.

Biomonitoring Assessment of Toxic and Trace Elements in Sterechinus neumayeri Sea Urchins from the Comandante Ferraz Station in Antarctica.

In the present study, sea urchin Sterechinus neumayeri tissues were used for the passive biomonitoring of toxic and trace elements at the Comandante Ferraz Station, Antarctica and compared to a pristine region (Botany). As, Ba, Br, Ca, Co, Cr, Fe, K, Na, Rb, Sc, Se and Zn concentrations were determined by instrumental neutron activation analysis (INAA), while toxic metals (Cd, Hg, Ni and Pb), and Cu were determined by atomic absorption spectrometry (GF-AAS). The findings were compared to other organisms commonly applied for biomonitoring purposes and to the sediment concentrations of each sampling region. Urchins from the Ferraz Station area presented higher Br, Co, Cr, Cs, K, Se and Zn levels than the pristine location. The results obtained herein suggest S. neumayeri can be applied to the biomonitoring of Cr and Zn. The present study also contributes to knowledge of the mineral composition of the sea urchin S. neumayeri.

Emerging contaminants (Rh, Pd, and Pt) in surface sediments from a Brazilian subtropical estuary influenced by anthropogenic activities.

The concentrations of Platinum (Pt), Rhodium (Rh) and Palladium (Pd) were evaluated from a highly impacted estuary in Brazil influenced by industrial pole, highway traffic and sewage outfall. The Santos-São Vicente region presents important economic activities derived from a largest harbor of Latin America and an industrial pole surrounded by intensive highway traffic. Values of Rh varied from 0.08 to 1.7 ng g-1 with highest values at stations impacted by domestic waste. Pt ranged from 0.15 to 40.3 ng g-1 with highest concentrations located close to the ferryboat traffic. Pd levels varied from 1.05 to 22.0 ng g-1 with values >5 ng g-1 in 50% of the stations. The spatial distribution of PGEs was not always directly associated with muddy sediments, because high PGE levels found even in sandy sediments. Pollution indexes, including anthropogenic factor (AF), geoaccumulation index (Igeo), Enrichment factor (EF), and Pollution Load Index (PLI) were used for evaluating contaminant potential. Based on EF, Igeo, and PLI, 50% of samples of the sediments from Santos-São Vicente Estuarine System (SSV) were classified with significant to strong PGE contamination. All stations on the Santos Channel (SC), São Vicente Channel (SVC) and Bertioga Channel (BC) had AF higher than 80% in at least one of PGE elements, as showed in station 2A, which presented AF <50% for Rh and Pd and 86% for Pt. Despite high anthropogenic enrichment, no correlations among PGE elements were observed in surface sediments. Only two stations presented Pd/Pt, Pt/Rh, and Pd/Rh typical ratios of auto catalyst (st. 14 and Piaçaguera) both located in the vicinity of highways. This could be due to the PGE deposition process in road dust, soil, and water as well as the biogeochemical cycling of PGEs involving organic metallic and inorganic complexes formed in the estuarine and seawaters.

Heavy Metals in Tissues of Blue Crabs Callinectes danae from a Subtropical Protected Estuary Influenced by Mining Residues.

This short note aims to report in detail a preliminary assessment of the concentrations of Cd, Hg and Pb in tissues of blue crabs Callinectes danae collected from the Cananéia-Iguape-Peruíbe estuarine complex (CIP), in the South of São Paulo State coast, Brazil. In October 2014, blue crabs were collected from CIP. Tissues were removed by dissection and metal determination was performed by GF-AAS and CV-AAS. According to statistical analysis, Pb and Cd concentrations in gills were significantly higher than those found in muscles and hepatopancreas, respectively. There were no significant differences in Hg concentrations between samples. Cd, Hg and Pb concentrations in gills and hepatopancreas were lower than those reported in a previous study performed at CIP. However, Cd concentration in hepatopancreas was higher than the Brazilian limit for consumption and new efforts to monitor Cd concentrations in C. danae tissues must be performed.

Implications on the Pb bioaccumulation and metallothionein levels due to dietary and waterborne exposures: The Callinectes danae case.

This study aimed to assess the bioaccumulation of Pb and induction of metallothionein-like proteins (MT) in Callinectes danae through single and combined dietary and waterborne exposures. Male C. danae individuals were collected in the south area of the Cananéia-Iguape-Peruíbe Protected Area (APA-CIP), in São Paulo State, Brazil. After an acclimatization period, exposure assays were performed during 7 and 14 days, at two Pb concentrations (0.5 e 2.0 µg/g) in 4 treatments: 1) control; 2) contaminated water only; 3) contaminated food only; 4) contaminated water and food. The results indicate that C. danae is highly tolerant to Pb exposure at the evaluated concentrations. In gills, Pb bioaccumulation is more dependent of water efflux and time of exposure (higher Pb values). However, pathways act simultaneously in the induction of MT expression in this tissue. The decreases in Pb accumulation in the combined treatments and MT increases after 14 days in gills suggests that these proteins play a detoxification function in the presence of Pb. In hepatopancreas, depending on the predominance of a certain pathway or combined pathways, accumulation occured at different times. For muscle tissue, bioaccumulation was observed due to contaminated water exposure, but not dietary exposure, probably because Pb concentrations were low.

The environmental impact of informal and home productive arrangement in the jewelry and fashion jewelry chain on sanitary sewer system.

The outsourcing informal home practices adopted in jewelry and fashion jewelry chain can cause toxic substance elimination in the effluents and raise a concern for its environmental impact. This study evaluates if this informal work alters the concentration of potentially toxic elements (PTEs: As, Cd, Cr total and Cr-VI, Cu, Hg, Ni, Pb, Sn, and Zn) in the sewage network. The sanitary sewage samples (n = 540) were collected in 15 manholes during two campaigns in three different areas of Limeira-SP, Brazil (industrial area, with informal work and without known industrial/informal activity). The sewage sludge (n = 12), raw (n = 12), and treated sewage (n = 12) were collected in two wastewater treatment plants (WWT: AS and TATU) operating with different treatment process. The PTE determination was performed by ICP-OES, direct mercury analysis, and UV-Vis spectroscopy. Cr-VI, Cu, Ni, and Zn were the only elements above the quantification limit. Four samples exceeded Cu or Zn values permitted to be discharged into sewage system; however, the concentration average was lower than that established by Brazilian legislation. A difference was found between values above and below the 75th percentile for campaign and total organic carbon values (p < 0.015). The AS-treated sewage presented low concentrations of Cu (p < 0.05), Zn (p = 0.02), and Ni (p = 0.01) compared to treated sewage from TATU. In the sludge samples, the Cu means exceeded the limits of the Brazilian legislation (1500 mg kg-1) and the Zn results were very close to the limits (2800 mg kg-1). The heterogeneity of the results can indicate the sporadic nature of the PTE's sanitary disposal. PTEs used in jewelry and fashion jewelry chain may precipitate on the sludge, where presented high concentrations of Cu and Zn which require controlled destination.

GPX1 Pro198Leu polymorphism and GSTM1 deletion do not affect selenium and mercury status in mildly exposed Amazonian women in an urban population.

Mercury is potent toxicant element, but its toxicity can be reduced by forming a complex with selenium for safe excretion. Considering the impact of mercury exposure in the Amazon region and the possible interaction between these two elements, we aimed to assess the effects of Pro198Leu polymorphism to GPX1 and GSTM1 deletion, on mercury levels in a population from Porto Velho, an urban locality in the Brazilian Amazon region. Two hundred women from the capital city of Rondônia state were recruited for this study with 149 deemed suitable to participate. We assessed dietary intake using 24-hour recall. Selenium levels in plasma and erythrocytes were measured using hydride generation quartz tube atomic absorption spectroscopy and total hair mercury using cold vapor atomic absorption spectrometry. Oxidative stress parameters (GPx activity, oxygen radical absorbency capacity [ORAC] and malondialdehyde [MDA]) were also analyzed. All participants were genotyped for Pro198Leu polymorphism and GSTM1 deletion. We observed that this population presented high prevalence of selenium deficiency, and also low levels of mercury, likely due to food habits that did not include selenium-rich food sources or significant consumption of fish (mercury biomagnifiers) regularly. Univariate statistical analysis showed that Pro198Leu and GSTM1 genotypes did not affect selenium and mercury levels in this population. Pro198Leu polymorphism and GSTM1 deletion had no effect on mercury levels in mildly exposed people, suggesting these genetic variants impact mercury levels only in highly exposed populations.

Selenium status and hair mercury levels in riverine children from Rondônia, Amazonia

Objective: Riverine communities in Rondônia State are exposed to high selenium (Se) content in their diet because of the high-selenium soils identified in the Amazon. However, the Amazonian population has a high mercury (Hg) exposure because this metal accumulates in the soil. Because children are more vulnerable to Hg toxicity, the aim of this study was to evaluate and correlate Se status and hair Hg levels in riverine children (aged 3–9 y) living in two different locations in Rondônia State: Demarcação area (DA) and Gleba do Rio Preto (GRP)...

Selenium status and hair mercury levels in riverine children from Rondônia, Amazonia.

OBJECTIVE: Riverine communities in Rondônia State are exposed to high selenium (Se) content in their diet because of the high-selenium soils identified in the Amazon. However, the Amazonian population has a high mercury (Hg) exposure because this metal accumulates in the soil. Because children are more vulnerable to Hg toxicity, the aim of this study was to evaluate and correlate Se status and hair Hg levels in riverine children (aged 3-9 y) living in two different locations in Rondônia State: Demarcação area (DA) and Gleba do Rio Preto (GRP). METHODS: Se levels were assessed using hydride generation quartz tube atomic absorption spectroscopy; total hair Hg levels were assessed using cold vapor atomic absorption spectrometry. Dietary intake was evaluated through a 24-h food record and a food frequency questionnaire. RESULTS: Forty-two children participated in this study. Eighty-four percent of the children from DA showed low plasma Se. Conversely, all children from GRP presented plasma Se levels above the reference values. Forty-five percent of the children from DA presented low erythrocyte levels, and 55% of the children from GRP showed concentration in erythrocyte above the reference values. The mean Se intake was 41.8 µg/d in DA and 179.0 µg/d in GRP. High hair Hg levels were observed in children from both the DA and GRP (3.57 ± 1.86 and 6.24 ± 5.89, respectively). CONCLUSIONS: Children from both riverine communities are likely to present altered Se status according to their dietary intake. Additionally, these children are highly exposed to Hg, mainly through fish consumption, and the toxicity of this metal may cause metabolic damage.

Mercúrio e Metilmercúrio em cabelos de crianças e em peixes mais consumidos em Cubatão, Estado de São Paulo, Brasil / Mercury and Methylmercury in the children hair and fish mostly consumed in Cubatão, São Paulo State, Brazil

This study evaluated Hg and MeHg concentrations in fish muscle and children hair from Cubatão, using asstrategies: i) Hg and MeHg determinations in the mostly consumed fish species, ii) Hg and MeHg determinationsin 93 children hair samples (from 04 to 14 years old), and iii) analysis on the children diet consumptionquestionnaire answered by the respective parents. The results obtained in a similar study in Cananeia were usedas references. These two regions show different environmental anthropogenic impacts and distinct eating habits.The quantity and the frequency of fish consumption were the most important factors of Hg bioaccumulation inchildren hair. In both cities, 95 % of mercury contents in hair were >1 mg.kg-1 (US EPA reference) in analyzedchildren, and MeHg were between 67 and 83 % of total Hg. The median for total Hg concentration in fishmuscle (wet basis) ranged from 10 to 179 μg.kg-1 for Cananéia and 10 to 181 μg.kg-1 for Cubatão, values lowerthan the Brazilian limits for Hg in fish. Considering the Hg contents detected in the mostly consumed fish andhair, they indicate that the children are not at risk for Hg and MeHg contamination...

Este estudo avaliou a concentração de Hg e MeHg em amostras de peixes e de cabelos de crianças de Cubatão, usando-se como estratégia: i) Hg total e MeHg em peixes mais consumidos; ii) Hg total e MeHg em cabelos de 93 crianças (04 a 14 anos); iii) análise do inquérito alimentar respondido pelos pais. Os dados obtidos em estudo similar realizado em Cananéia foram usados como referência. Essas duas regiões estuarinas, sob diferentes graus de impacto ambiental, apresentam diferentes hábitos alimentares. A quantidade e a frequência de consumo de peixes foram os fatores mais importantes na bioacumulação de Hg nos cabelos. Em ambas as cidades, 95 % das concentrações de Hg total nos cabelos foram abaixo de 1 mg.kg-1 (limite US EPA) e o percentual de MeHg ocorreu entre 67 e 83 % em relação ao teor de Hg total. As medianas para Hg total nos músculos (base úmida) variaram de 10 a 179 μg.kg-1 para peixes de Cananéia e 10 a 181 μg.kg-1 de Cubatão, inferiores ao limite da legislação brasileira para Hg. A partir dos teores para Hg total e MeHg em peixes mais consumidos e cabelos, as crianças parecem não estar em risco de contaminação...

Caracterização físico-química do suco de açaí de Euterpe precatoria Mart. oriundo de diferentes ecossistemas amazônicos / Physicochemical characterization of acai juice of Euterpe precatoria Mart. from different amazonian ecosystems

Os frutos do açaizeiro (Euterpe precatoria Mart.) procedentes de diferentes ecossistemas amazônicos foram processados para a obtenção de suco. O produto foi avaliado quanto à composição centesimal (umidade, cinzas, lipídeos, proteína, glicídios e fibra alimentar), minerais, ácidos graxos e antocianinas. Os frutos foram comparados quanto ao peso, constatando-se uma variação significativa de 1,1 a 2,0 g entre eles. Com relação ao suco, verificou-se baixa concentração de proteína e alto teor de energia devido, principalmente, à presença de lipídeos cuja concentração variou de 4,24 a 9,74 por cento. Dentre os minerais, o potássio foi o mais abundante com teores na faixa de 73,78 a 376,69 mg 100 g-¹ (do suco), seguido do cálcio (15,99 a 57,85 mg 100g-¹). O ferro foi encontrado em concentrações minoritárias, na ordem de 0,43 a 1,2 mg 100g-¹. Com relação aos ingredientes funcionais, o suco de açaí apresentou concentrações importantes de fibra alimentar (2,37 a 7,8 por cento), e antocianinas, variando de 128,4 mg 100 g-¹ , nos frutos de coloração verde, procedentes de Parintins, até 868,9 mg 100 g-¹ nas amostras de Manaquiri (base seca). Na fração lipídica, destacou-se ainda a presença do ácido graxo oleico (18:1), com porcentagem média de 68,2 por cento no total de ácidos graxos, seguido do ácido palmítico (16:0) com 17,5 por cento. Tais resultados reforçam o potencial do açaí como fonte de energia, lipídeos, fibra alimentar, antocianinas, ácido graxo monoinsaturado e minerais. O presente estudo irá contribuir para a ampliação da tabela de composição química de alimentos e, consequentemente, auxiliar nos programas de melhoramento genético, mercado e inclusão social.

The fruit of açaí (Euterpe precatoria Mart.) from different Amazon ecosystems were processed to obtain the juice. The juice obtained from each ecosystem was evaluated for proximate composition (moisture, ash, lipids, protein, carbohydrates and dietary fiber), minerals, fatty acids and anthocyanins. The fruits prior to processing were compared in terms of weight, having noticed a significant variation from 1.1 to 2.0 g. Concerning to the juice, there was a low concentration of protein and high in energy, mainly due to the presence of lipids with a range from 4.24 to 9.74 percent. Among the minerals, potassium was the most abundant ranging from 73.78 to 376.69 mg 100 g-¹ (per of juice), followed by calcium (from 15.99 to 57.85 mg 100g-¹.). Iron presented minority concentrations from 0.43 to 1.2 mg 100g-¹. With regard to functional ingredients, the acai juice showed significant concentrations of dietary fiber (2.37 to 7.8 percent), anthocyanins, ranging from 128.4 mg 100 g-¹ in fruits of green color coming from Parintins to 868.9 mg 100 g-¹ in samples of Manaquiri (dry basis). The lipid fraction showed high quantities of oleic fatty acid (18:1), with average percentage of 68.2 percent in total fatty acids, followed by palmitic acid (16:0) with 17.5 percent. These results reinforce the potential of acaí as a source of energy, fat, dietary fiber, anthocyanins, monounsaturated fatty acid and mineral elements. The present study will contribute to the expansion of table food composition and to aid in the genetic improvement program, market and social inclusion.

Cooking process evaluation on mercury content in fish / Influência do processo de cocção no teor de mercúrio em peixes

This study evaluated different cooking processes (roasted, cooked and fried) on total mercury (Hg) content in fish species most consumed by Manaus residents and surrounding communities, Amazon region. The results obtained for total Hg in natura and after the three types of preparation (roasted, cooked and fried) for 12 fish species showed a significant Hg concentration variation. In the present study the cooked and frying processes resulted in higher Hg losses for Pacu, Pescada, Jaraqui, Curimatã, Surubin and Aruanã fish species, most of them presenting detritivorous and carnivorous feeding habits. The higher Hg losses in the roasting process occurred for Sardinha, Aracu, Tucunaré, Pirapitinga, Branquinha and Tambaqui fish species, most of them being omnivorous and herbivorous fish species. Some micronutrients (Ca, Fe, K, Na, Se and Zn) in fish species in natura were also determined in order to perform a nutritional evaluation regarding these micronutrients.

O presente estudo avaliou três diferentes processos de cocção (assado, cozido e frito) e sua relação com o teor de mercúrio total (Hg) em espécies de peixes comumente consumidas pela população de Manaus e comunidades vizinhas da região Amazônica. Os resultados obtidos para Hg total in natura (antes) e após os três tipos de preparo (assado, cozido e frito) para as 12 espécies de peixes selecionadas apresentaram uma significativa variação na concentração. Os processos de cozimento e fritura resultaram em maiores perdas de Hg para as espécies Pacu, Pescada, Jaraqui, Curimatã, Surubin e Aruanã sendo a maioria delas classificadas como espécies detritívoras e carnívoras. As maiores perdas de Hg no processo assado ocorreram para as espécies Sardinha, Aracu, Tucunaré, Pirapitinga, Branquinha e Tambaqui, a maioria classificadas como espécies omnivoras e herbivoras. Alguns micronutrientes (Ca, Fe, K, Na, Se e Zn) nas espécies de peixes in natura foram determinados com o objetivo de fazer uma avaliação nutricional em relação a esses constituintes.

Determinação de mercúrio e metilmercúrio em amostras de cabelo e peixes / Determination of mercury and methylmercury in fish and hair samples

A Espectrometria de Absorção Atômica com Geração de Vapor Frio (CVAAS) está entre os métodos mais utilizados atualmente para a determinação de mercúrio (Hg) e metilmercúrio (MeHg) em materiais biológicos devido a vantagens, tais como: facilidade de operação, rápida resposta analítica, boa sensibilidade e baixo custo. Neste estudo apresentam-se os resultados obtidos no programa de intercomparação da Agência Internacional de Energia Atômica (IAEA) o World-Wide Intercomparison Exercise for the Determination of Trace Elements and Methylmercury in Tuna Fish Flesh Homogenate (IAEA-436), realizado no período de outubro de 2004 a julho de 2005. A precisão e a exatidão do método para determinação de Hg e MeHg foram verificadas por meio da análise de materiais de referência com valores certificados para ambos. Os resultados obtidos apresentaram boa precisão e exatidão, com desvio padrão relativo de 2,2 a 10 % e erro relativo, de 0,4 a 12% para MeHg e desvio padrão relativo de 2,6 a 11,7% e erro relativo, de 0,9 a 3,11%, para Hg. O método apresentado mostrou-se adequado para determinação de baixos níveis destes contaminante sem amostras de cabelo e peixe e pode ser usado em estudos relacionados aos efeitos do Hg e suas espécies na saúde do ser humano.

Mercury and methylmercury content, fatty acids profile, and proximate composition of consumed fish in Cananéia, São Paulo, Brazil

Fifty three individuals of four most commonly consumed fish species by the Cananéia city population, in São Paulo, Brazil, were analyzedto determine total mercury (Total Hg) and methylmercury (MeHg) levels, as well as, proximate composition and fatty acid profile. Themuscle of three carnivorous species Centropomus parallelus (Fat snook), Macrodon ancylodon (King weakfish) and Micropogonias furnieri(Whitemouth croaker), and one planktivorous species Mugil platanus (Mullet) were analyzed. MeHg and Total Hg determinations wereperformed by Cold Vapour Atomic Absorption Spectrometry (CV AAS). Fatty acid profile was determined by gas chromatography (GC) whilst AOAC methods were used for proximate analysis. The total Hg results (interval) in wet weight basis were: Whitemouth croaker(114–442 μg kg-1), Fat snook (15-178 μg kg-1), King weakfi sh (12-100 μg kg-1) and Mullet (<10–25 μg kg-1), and none of the fish species exceeded the Brazilian legislation limits. MeHg values were below FAO/WHO (2007) recommendations. In nutritional terms, the resultsfor proximate composition for all four fish species proved to be an excellent protein source with very low lipid content as was expected. Fatty acids of all fish species were adequate. Total polyunsaturated fatty acid contents varied from 21.9% (Micropogonias furnieri) to26.4% (Mugil platanus). For the n-3 family, Macrodon ancylodon presented the highest value (20.9%) and Micropogonias furnieri thelowest one (15.8%). Mugil platanus (Mullet) species also showed good levels for all parameters analyzed and very low concentrations of contaminants, indicating it as a good nutritional choice in terms of risks and benefits.