Potentially toxic trace elements in the muscle of coastal South American fish: Implications for human consumption and health risk assessment.

Micropogonias furnieri and Urophycis brasiliensis are two coastal demersal fish species distributed in the southwestern Atlantic Ocean. Considering that many coastal areas in the southwestern Atlantic Ocean suffer from anthropogenic pressure, the aim of this study was to assess the level of potentially toxic trace elements (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Se, Sr, V and Zn) in the muscle of coastal species, and evaluated the human health risk related to the consumption of muscle. Mercury, inorganic As (Asi), V, and Se showed a higher contribution to the total THQ. Considering two possible scenarios, Asi represents 1 % or 5 % of the total As, the total THQ was <1 for general population and of some health concerns for fishermen population (Total THQ > 1; 5 % Asi). Consequently these results show the importance of quantifying As species in muscle to generate more reliable risk estimates for human health.

Selenium speciation in soils using flow injection hydride generation atomic absorption spectrometry with on-line removal of organic matter interferences.

A method based on flow injection hydride generation atomic absorption spectrometry (FI-HGAAS) with an on-line pre-reduction of Se(VI) to Se(IV) was developed and optimized to determine phosphate-extractable Se (0.1 M phosphate buffer KH2PO4/K2HPO4 at pH 7). The extracted fraction involves water-soluble Se (i.e. the most mobile Se fraction) and exchangeable Se (i.e. sorbed onto soil component surface). Kinetic discrimination mechanisms allowed the complete removal of interferences caused by organic matter due to the formation of humic substances (HS)-Se(IV) complexes observed when batch pre-reduction processes were used. Se(IV) and Se(VI) recoveries ranged 95-105% at a fortification level of 150 µg kg-1. The pre-reduction was efficiently carried out in 20 s in a 6 M HCl medium at 100 °C. Results from phosphate-extractable fractions were comparable to those obtained by ICP-MS. Se bound to organic matter was released digesting the remaining material from the phosphate buffer extraction with 0.1 M K2S2O8. Detection and quantification limits were 15 µg kg-1 Se and 50 µg kg-1 Se, respectively, in each fraction. The methodology was applied to 10 agricultural soils from Argentina with total Se concentration levels between 130 µg kg-1 and 419 µg kg-1.

First evaluation of novel potential synergistic effects of glyphosate and arsenic mixture on Rhinella arenarum (Anura: Bufonidae) tadpoles.

The toxicity of glyphosate-based herbicide (GBH) and arsenite (As(III)) as individual toxicants and in mixture (50:50 v/v, GBH-As(III)) was determined in Rhinella arenarum tadpoles during acute (48 h) and chronic assays (22 days). In both types of assays, the levels of enzymatic activity [Acetylcholinesterase (AChE), Carboxylesterase (CbE), and Glutathione S-transferase (GST)] and the levels of thyroid hormones (triiodothyronine; T3 and thyroxine; T4) were examined. Additionally, the mitotic index (MI) of red blood cells (RBCs) and DNA damage index were calculated for the chronic assay. The results showed that the LC50 values at 48 h were 45.95 mg/L for GBH, 37.32 mg/L for As(III), and 30.31 mg/L for GBH-As(III) (with similar NOEC = 10 mg/L and LOEC = 20 mg/L between the three treatments). In the acute assay, Marking's additive index (S = 2.72) indicated synergistic toxicity for GBH-As(III). In larvae treated with GBH and As(III) at the NOEC-48h (10 mg/L), AChE activity increased by 36.25% and 33.05% respectively, CbE activity increased by 22.25% and 39.05 % respectively, and GST activity increased by 46.75% with the individual treatment with GBH and by 131.65 % with the GBH-As(III) mixture. Larvae exposed to the GBH-As(III) mixture also showed increased levels of T4 (25.67 %). In the chronic assay at NOEC-48h/8 (1.25 mg/L), As(III) and GBH-As(III) inhibited AChE activity (by 39.46 % and 35.65%, respectively), but did not alter CbE activity. In addition, As(III) highly increased (93.7 %) GST activity. GBH-As(III) increased T3 (97.34%) and T4 (540.93%) levels. Finally, GBH-As(III) increased the MI of RBCs and DNA damage. This study demonstrated strong synergistic toxicity of the GBH-As(III) mixture, negatively altering antioxidant systems and thyroid hormone levels, with consequences on RBC proliferation and DNA damage in treated R. arenarum tadpoles.

National short-term dietary exposure assessment of a selected group of pesticides in Argentina.

An evaluation of acute dietary exposure to pesticide residues, applying deterministic and stochastic methods, was performed for a selected group of pesticides in two representative age groups from Argentina. Thus, 28 active ingredients (a.i.) and 75 food items were evaluated for the group of 2-5-year-old children, while 9 a.i. and 59 food items were considered for the 10-49-year-old women group. A deterministic assessment was conducting following the Food and Agriculture Organization (FAO) and World Health Organization (WHO) procedure but using the national maximum residue limits (MRLs) as pesticide residue concentration data, while in the stochastic approach, a theoretical distribution modeled with the available information was used. Food consumption data were obtained from the 2004-2005 comprehensive national nutrition and health survey. The risk was estimated by comparing the short-term dietary exposure with the acute reference dose (ARfD) values for each pesticide-food combination evaluated. In the deterministic assessment, 173 (39.1%) and 40 (31.3%) combinations exceeded the ARfD thresholds for the 2-5-year-old children and 10-49-year-old women groups, respectively. This conservative study generated relevant information as a first stage of acute dietary risk assessment in Argentina.

Comprehensive estimate of the theoretical maximum daily intake of pesticide residues for chronic dietary risk assessment in Argentina.

A chronic dietary risk assessment for pesticide residues was conducted for four age groups of the Argentinian population following the procedure recommended by the WHO. The National Theoretical Maximum Daily Intake (NTMDI) for 308 pesticides was calculated for the first time, using the Maximum Residue Limits (MRLs) from several Argentinean regulations and food consumption data from a comprehensive National Nutrition and Health Survey. The risk was estimated by comparing the TMDI with the Acceptable Daily Intakes (ADI) identified by various sources. Furthermore, for each of the compounds with a TMDI >65% of the ADI, a probabilistic analysis was conducted to quantify the probability of exceeding the ADI. In this study 27, 22, 10, and 6 active ingredients (a.i.) were estimated to exceed the 100% of the ADI for the different population groups: 6-23 month-old children, 2-5 year-old children, pregnant women, and 10-49 year-old women, respectively. Some of these ADI-exceeding compounds (carbofuran, diazinon, dichlorvos, dimethoate, oxydemeton-methyl and methyl bromide) were found in all four of these groups. Milk, apples, potatoes, and tomatoes were the foods that contributed most to the intake of these pesticides. The study is of primary importance for the improvement of risk assessment, regulations, and monitoring activities.

Total arsenic in selected food samples from Argentina: Estimation of their contribution to inorganic arsenic dietary intake.

An optimized flow injection hydride generation atomic absorption spectroscopy (FI-HGAAS) method was used to determine total arsenic in selected food samples (beef, chicken, fish, milk, cheese, egg, rice, rice-based products, wheat flour, corn flour, oats, breakfast cereals, legumes and potatoes) and to estimate their contributions to inorganic arsenic dietary intake. The limit of detection (LOD) and limit of quantification (LOQ) values obtained were 6µgkg(-)(1) and 18µgkg(-)(1), respectively. The mean recovery range obtained for all food at a fortification level of 200µgkg(-)(1) was 85-110%. Accuracy was evaluated using dogfish liver certified reference material (DOLT-3 NRC) for trace metals. The highest total arsenic concentrations (in µgkg(-)(1)) were found in fish (152-439), rice (87-316) and rice-based products (52-201). The contribution to inorganic arsenic (i-As) intake was calculated from the mean i-As content of each food (calculated by applying conversion factors to total arsenic data) and the mean consumption per day. The primary contributors to inorganic arsenic intake were wheat flour, including its proportion in wheat flour-based products (breads, pasta and cookies), followed by rice; both foods account for close to 53% and 17% of the intake, respectively. The i-As dietary intake, estimated as 10.7µgday(-)(1), was significantly lower than that from drinking water in vast regions of Argentina.

Determination of selenium in selected food samples from Argentina and estimation of their contribution to the Se dietary intake.

An optimised FI-HGAAS method was applied to determine the total selenium concentrations in selected high consumption food (fish, beef, chicken, milk, rice, wheat flour, egg) and to estimate their contribution to the Argentinean dietary intake, whose information is scarce nowadays. Through several optimisation steps a suitable method was achieved showing satisfactory figures of merit for all matrices. Average recovery was 96%, RSD<5%, LODs ranged 2.0-7.0 µg kg(-1) and the accuracy was assessed using DOLT-3 NRC certified reference material. Meat and eggs showed the highest values (in µg kg(-1), beef: 42-153; chicken: 62-205; fish: 94-314; canned tuna: 272-282; eggs: 134-217), minor values were found for wheat flour (22-42), rice: (<22), pasta (47-64) and milk (<7-9). An estimated intake of 32 and 24 µg day(-1) for adult men and women, respectively, suggested a deficient Se intake, leading to further comprehensive surveys of Se occurrence in Argentina.

Determination of As(III) and total inorganic As in water samples using an on-line solid phase extraction and flow injection hydride generation atomic absorption spectrometry.

A simple and robust on-line sequential injection system based on solid phase extraction (SPE) coupled to a flow injection hydride generation atomic absorption spectrometer (FI-HGAAS) with a heated quartz tube atomizer (QTA) was developed and optimized for the determination of As(III) in groundwater without any kind of sample pretreatment. The method was based on the selective retention of inorganic As(V) that was carried out by passing the filtered original sample through a cartridge containing a chloride-form strong anion exchanger. Thus the most toxic form, inorganic As(III), was determined fast and directly by AsH(3) generation using 3.5 mol L(-1) HCl as carrier solution and 0.35% (m/v) NaBH(4) in 0.025% NaOH as the reductant. Since the uptake of As(V) should be interfered by several anions of natural occurrence in waters, the effect of Cl(-), SO(4)(2-), NO(3)(-), HPO(4)(2-), HCO(3)(-) on retention was evaluated and discussed. The total soluble inorganic arsenic concentration was determined on aliquots of filtered samples acidified with concentrated HCl and pre-reduced with 5% KI-5% C(6)H(8)O(6) solution. The concentration of As(V) was calculated by difference between the total soluble inorganic arsenic and As(III) concentrations. Detection limits (LODs) of 0.5 µg L(-1) and 0.6 µg L(-1) for As(III) and inorganic total As, respectively, were obtained for a 500 µL sample volume. The obtained limits of detection allowed testing the water quality according to the national and international regulations. The analytical recovery for water samples spiked with As(III) ranged between 98% and 106%. The sampling throughput for As(III) determination was 60 samplesh(-1). The device for groundwater sampling was especially designed for the authors. Metallic components were avoided and the contact between the sample and the atmospheric oxygen was carried to a minimum. On-field arsenic species separation was performed through the employ of a serial connection of membrane filters and anion-exchange cartridges. Advantages derived from this approach were evaluated. HPLC-ICPMS was employed to study the consistency of the analytical results.