Detection of hormones in surface and drinking water in Brazil by LC-ESI-MS/MS and ecotoxicological assessment with <Emphasis Type="Italic">Daphnia magna</Emphasis>

The growing use of pharmaceutical drug is mainly due to several diseases in human and in animal husbandry. As these drugs are discharged into waterways via wastewater, they cause a major impact on the environment. Many of these drugs are hormones; in which even at low concentrations can alter metabolic and physiological functions in many organisms. Hormones were found in surface water, groundwater, soil, and sediment at concentrations from nanograms to milligrams per liter of volume—quantities known to cause changes in the endocrine system of aquatic organisms. This study aimed to develop a methodology for hormone detection (estriol, estrone, 17β-estradiol, 17α-ethinylestradiol, progesterone, and testosterone) on surface and treated water samples. Sample toxicity was assessed by ecotoxicology tests using Daphnia magna. A liquid chromatograph coupled to a mass spectrometer with an electrospray ionization source (LC-ESI-MS/MS) was used for the analysis. The results showed that samples were contaminated by the hormones estriol, estrone, progesterone, 17β-estradiol, and 17α-ethinylestradiol during the sampling period, and the highest concentrations measured were 90, 28, 26, 137, and 194 ng·L^?1, respectively. This indicates the inflow of sewage containing these hormones at some points in the Piracicaba River in the State of Sao Paulo—Brazil. Results indicated little toxicity of the hormone estriol in D. magna, indicating that chronic studies with this microcrustacean are necessary.     

Phosphorus removal by a fixed-bed hybrid polymer nanocomposite biofilm reactor

Eutrophication is one of the main challenges regarding the ecological quality of surface waters, phosphorus bioavailability being its main driver. In this context, a novel hybrid polymer nanocomposite (HPN-Pr) biofilm reactor aimed at integrated chemical phosphorus adsorption and biological removal was conceived. The assays pointed to removal of 1.2 mg P/g of reactive phosphorus and 1.01 mg P/g of total phosphorus under steady-state conditions. A mathematical adsorption–biological model was applied to predict reactor performance, which indicated that biological activity has a positive effect on reactor performance, increasing the amount of reactive phosphorus removed.     

Factors affecting RPSI in imposex monitoring studies using Nucella lapillus (L.) as bioindicator

Nucella lapillus (L.) is a marine gastropod mollusc widely used as a bioindicator of TBT pollution in the North Atlantic coastlines. The species reproductive cycle and the male penis length seasonal/spatial variation were studied at a single site at Aveiro seashore (NW Portugal) between December 2005 and June 2007. The main objective of this work is to assess if the "Relative Penis Size Index" (RPSI)--an important imposex assessment index--varies seasonally and spatially in the same sampling site and how this can affect results obtained in imposex monitoring programmes. Animals able to reproduce were found every month but a seasonal pattern in N. lapillus reproductive cycle was evident. Female gametogenic maturation varied seasonally and a decrease in capsule gland volume and condition factor occurred in late summer/early autumn. The gametogenesis in males did not show a significant seasonal variation as in females but the condition factor, penis length, amount of sperm and prostate volume also diminished in late summer/early autumn. On the other hand, males that were close to egg capsules clusters had larger penises than those far away from clusters. The temporal and spatial male penis length variation introduces a bias on imposex assessment results when using RPSI and the magnitude of the error involved is evaluated for different TBT pollution levels scenarios. We consider that RPSI provides interesting and complementary information that should not be excluded from monitoring programmes, but temporal or spatial comparisons of imposex should be based on other more reliable imposex indices like the VDSI.     

Precipitation of aragonite by calcitic bivalves in Mg-enriched marine waters

To understand the relative importance of biological versus physicochemical control over biomineralization, we have tested if the chemical composition of the medium (i.e., the Mg/Ca ratio) can change the mineralogy of mollusk shells. The shells of mollusks are made of calcite and/or aragonite, which are by far the most common CaCO₃ polymorphs. Several species of bivalves with predominantly calcitic shells have been cultivated in artificial seawater with a Mg/Ca molar ratio within the range of 8.3–9.2, well above the present value for seawater (5.2). Four out of six species used (the scallop Chlamys varia, the oyster Ostrea edulis, the saddle oyster Anomia ephippium and the mussel Mytilus edulis) survived long enough to secrete significant amounts of calcium carbonate. The deposits (sometimes extensive) formed on the interior shell surfaces were predominantly aragonitic. Three individuals of C. varia also increased their length by adding new shell at the margin. Contrary to the internal shell deposits, these margins were high-Mg calcite. This implies that the marginal mantle is able to exert a more strict control on the secreted mineral phase than the mantle facing the internal shell surface. This is the first report on an in vivo experimentally forced switch in bivalve shell mineralogy, from calcite to aragonite due to a change in water chemistry.     

Microbial fuel cell-induced production of fungal laccase to degrade the anthraquinone dye Remazol Brilliant Blue R

Environmental Chemistry Letters - The anthraquinone dye Remazol Brilliant Blue R is largely used in the textile industry. However, its removal from wastewaters is costly and complex. Many methods...     

Five years of formaldehyde and acetaldehyde monitoring in the Rio de Janeiro downtown area – Brazil

The fuel matrix used in Brazil is unique around the world. The intensive use of hydrated ethanol, gasohol (gasoline with 25% v/v of ethanol), compressed natural gas (CNG), and biodiesel leads to a peculiar composition of the urban atmosphere. From 1998 to 2002 an increase in formaldehyde levels was observed and since then, a reduction. This work presents a monitoring campaign that was executed from March 2004 to February 2009 by sampling at early morning on every sunny Wednesday for a total of 183 samples. The results indicate a strong reduction in formaldehyde levels from 2004 (average of 135.8 μg m^?3 with SD 28.4 μg m^?3) to 2009 (average of 49.3 μg m^?3 with SD 27.4 μg m^?3). The levels of acetaldehyde showed a slight reduction from 2004 (average of 34.9 μg m^?3 with SD 8.0 μg m^?3) to 2009 (average of 26.8 μg m^?3 with SD 11.5 μg m^?3). Comparing the results with the concurrent evolution of the fleet and of fuel composition indicates that the observed formaldehyde levels could be associated with the increase in ethanol use and in CNG use by engines with improved technology over the first converted CNG engines. Modelling studies using the OZIPR trajectory model and the SAPRC chemical mechanism indicate that formaldehyde is the main ozone precursor in Rio de Janeiro and acetaldehyde is the forth one.     

Environmental mutagenicity and toxicity caused by sodium metabisulfite in sea shrimp harvesting in Piauí, Brazil

Sodium metabisulfite is used in marine shrimp harvesting to prevent the occurrence of black spots. Shrimps are soaked in a sodium metabisulfite solution in ice, which is disposed of in sewages that run into marine canals, creating an environmental hazard. This study evaluates the toxicity and mutagenicity caused by sodium metabisulfite in sea waters and sediments collected in a shrimp farm in Cajueiro da Praia (Luis Correia), state of Piauí, Brazil, using the Allium cepa assay. Water and sediment samples were collected in the dry and in the rainy seasons, in three sites: upstream the shrimp farm (Site 1), at the point sodium metabisulfite is discharged (Site 2), and 100 m downstream the farm (Site 3). Three sample dilutions were used (50%, 25% and 10%) for all samples. A negative control (well water) and a positive control (copper sulfate 0.0006 mg mL⁻¹) were used in each experiment. At the end of the 72-h exposure period, onion roots were measured and removed. Mutagenicity analysis included the determination of mitotic index, chromosomal aberrations and the detection of micronuclei; analysis of root size and mitotic index were used as an index of toxicity. The A. cepa assay revealed that the water and sediments samples collected in the Piauí coast contaminated with sodium metabisulfite induce toxicity. The results demonstrate that the assay may be used as a regular tool in the analysis of water parameters in shrimp farms in the coast of Piauí state, and in strategies to preserve the region’s marine ecosystem.     

Voltammetric analysis of metallothioneins and copper (II) in fish for water biomonitoring studies

An major research area in environmental chemistry is the development of methods for the analysis of biomarkers. Metallothioneins are used as biomarkers in studies of heavy metals exposure in water, because metallothioneins are synthesized and accumulated when organisms are exposed to toxic concentrations of pollutants. In this work, simple and sensitive voltammetric methods were developed for metallothionein and copper (II) determinations in fish liver Lepomis gibbosus. Both analytical methodologies were optimized and applied to samples extracted from individuals previously submitted to sub-lethal toxicological trials with copper sulphate (CuSO₄) and cadmium chloride (CdCl₂). The obtained results showed that both methods are very precise, sensitive, and involve simple sample preparation processes. Moreover, metallothioneins showed better correlation with the toxic exposure than Cu²⁺. To the best of our knowledge, this is the first time that hepatic metallothioneins and Cu²⁺ contents are voltammetrically determined in order to be compared in their function as heavy metal biological indicators.     

EDDS and EDTA-enhanced zinc accumulation by Solanum nigrum inoculated with arbuscular mycorrhizal fungi grown in contaminated soil

The effect of two different chelating agents [EDTA and EDDS (S,S-ethylenediaminedissucinic acid)] on Zn tissue accumulation in Solanum nigrum L. grown in a naturally contaminated soil was assessed. Under those conditions, the response of the plant to the inoculation with two different isolates of arbuscular mycorrhizal fungi (AMF)--Glomus claroideum and Glomus intraradices--was also studied. Plants grown in the local contaminated soil (Zn levels of 433mg kg(-1)) accumulated up to 1191mg kg(-1) of Zn in the roots, 3747mg kg(-1) in the stems and 3409mg kg(-1) in the leaves. S. nigrum plants grown in the same soil spiked with extra Zn (Zn levels of 964mg kg(-1)) accumulated up to 4735, 8267 and 7948mg Zn kg(-1) in the leaves, stems and roots, respectively. The addition of EDTA promoted an increase in the concentration of Zn accumulated by S. nigrum of up to 231% in the leaves, 93% in the stems and 81% in the roots, while EDDS application enhanced the accumulation in leaves, stems and roots up to 140, 124 and 104%, respectively. In the stems, the presence of Zn was predominantly detected in the cortex collenchyma cells, the starch sheath and the internal phloem and xylem parenchyma, and the addition of chelating agents did not seem to have an effect on the localisation of accumulation sites. The devise of a chelate-enhanced phytoextraction strategy, using chelating agents and AMF, is discussed.     

Sub-tropical urban environment affecting content and composition of non-structural carbohydrates of Lolium multiflorum ssp. italicum cv. Lema

This study analyzed the relationship between environmental factors, especially air pollution and climatic conditions, and non-structural carbohydrates (NSC) in plants of Lolium multiflorum exposed during 10 consecutive periods of 28 days at a polluted site (Congonhas) and at a reference site in São Paulo city (Brazil). After exposure, NSC composition and leaf concentrations of Al, Fe, Cu, Zn, Pb and Cd were measured. The seasonal pattern of NSC accumulation was quite similar in both sites, but plants at Congonhas showed higher concentrations of these compounds, especially fructans of low and medium degree of polymerization. Regression analysis showed that NSC in plants growing at the polluted site were explained by variations on temperature and leaf concentration of Fe (positive effect), as well as relative humidity and particulate material (negative effect). NSC in the standardized grass culture, in addition to heavy metal accumulation, may indicate stressing conditions in a sub-tropical polluted environment.