Relationship Between Biogenic Amines and Free Amino Acid Contents of Wines and Musts from Alentejo (Portugal)

The concentration of biogenic amines and free amino acids was studied in 102 Portuguese wines and 18 musts from Alentejo demarcated (D.O.C.) regions. Most wines were commercial, except for 38 monovarietals obtained by micro vinification. Musts from the varieties used to produce the latter wines were also studied. Both biogenic amines and free amino acids were analyzed by HPLC using fluorescence detection for their o-phthalaldehyde/fluorenylmethyl chloroformate (OPA/FMOC) derivatives. The most significant amines (average 10.8 mg/L for histamine+tyramine in red, and 7.4 mg/L for white wines) were found to be present at low levels and, although no important relationship between each individual biogenic amine could be obtained, the total amine content depends significantly on the assimilable amino acid content in wine.     

Organo-tins in sediments and mussels from the Sado estuarine system (Portugal)

Analyses of methyl- and butyl-tin levels in freshwater, estuarine and marine sediments from the Sado estuarine system, and in mussels (Mytilus galloprovincialis) from its adjacent coast, have been performed in order to detect the contaminated areas. The main inputs of tributyl-tin (TBT), along with degradation products di- and monobutyl-tin (DBT and MBT), were detected in the estuarine zone, due to high discharge from shipyards located in this area. These levels are sometimes very high, ranging from 235 to 12,200 ng g(-1) total butyl-tins in sediments. Such inputs lead to higher bioconcentration values in mussels in the estuarine zone, as well as in a harbour located along the adjacent coast. The bioconcentration of organo-tins in mussel tissues could be enhanced in estuarine turbid waters, due to an ingestion of butyl-tins adsorbed onto fine particles, in comparison with non-turbid coastal waters. Debutylation processes occur in both sediments and mussel tissues; in organisms, these processes may lead to the formation of inorganic tin, which may be methylated differently according to the period of the year.     

Acid azo dye degradation by free and immobilized horseradish peroxidase (HRP) catalyzed process

Acid azo (Acid Black 10 BX) dye removal by plant based peroxidase catalyzed reaction was investigated. Horseradish peroxidase (HRP) was extracted from horseradish roots and its performance was evaluated in both free and immobilized form. HRP showed its ability to degrade the dye in aqueous phase. Studies are further carried out to understand the process parameters such as aqueous phase pH, H2O2 dose, dye and enzyme concentrations during enzyme-mediated dye degradation process. Experimental data revealed that dye (substrate) concentration, aqueous phase pH, enzyme and H2O2 dose play a significant role on the overall enzyme-mediated reaction. Acrylamide gel immobilized HRP showed effective performance compared to free HRP and alginate entrapped HRP. Alginate entrapped HRP showed inferior performance over the free enzyme due to the consequence of non-availability of the enzyme to the dye molecule due to polymeric immobilization. Standard plating studies performed with Pseudomonas putida showed enhanced degradation of HRP catalyzed dye compared to control.     

Recycling of biogenic hydroxyapatite (HAP) for cleaning of lead from wastewater: performance and mechanism

Environmental Science and Pollution Research - In China, the utilization and recycling of chicken waste have become a significant environmental issue. In this study, we investigate the efficacy of...     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

Evaluation of the toxicity of two soils from Jales Mine (Portugal) using aquatic bioassays

Soil contamination can be one path for streams and groundwater contamination. As a complement of chemical analysis and total contaminants determination, bioassays can provide information on the bioavailable fraction of chemical compounds, focusing on the retention and habitat function of soils. In this study the evaluation of the toxicity of two soils from the abandoned Jales Mine (Portugal) regarded both functions. The buffer capacity of soils was tested with bioassays carried out using the cladoceran Daphnia magna and the marine bacteria Vibrio fischeri. The habitat function of soils was evaluated with the reproduction bioassay with the collembolan Folsomia candida. The Microtox solid-phase test was performed with V. fischeri using soil as test medium, and soil elutriates were extracted to perform the Microtox basic test, and an immobilization and reproduction bioassay with D. magna. The marine bacteria showed high sensitivity to the soil with low heavy metal content (JNC soil) and to JNC soil elutriates, while the soil with highest heavy metal content (JC soil) or soil elutriates exposure did not cause any toxic effect. In the bioassays with D. magna, organisms showed sensitivity to JNC and also to JC soil elutriates. Both mobilization and reproduction features were inhibited. The bioassay with F. candida did not reflect any influence of the contaminants on their reproduction. Although JNC soil presented lower heavy metal contents, elutriates showed different patterns of contamination when compared to JC soil and elutriates, which indicates different retention and buffer capacities between soils. Results obtained in this study underlined the sensitivity and importance of soil elutriate bioassays with aquatic organisms in the evaluation strategy in soil ERA processes.     

Accumulation and biological cycling of heavy metal in four salt marsh species, from Tagus estuary (Portugal)

Pools of Zn, Cu, Cd and Co in leaf, stem and root tissues of Sarcocornia fruticosa, Sarcocornia perennis, Halimione portulacoides and Spartina maritima were analyzed on a bimonthly basis, in a Tagus estuary salt marsh. All the major concentrations were found in the root tissues, being the concentrations in the aboveground organs neglectable for sediment budget proposes, as seen by the low root-aboveground translocation. Metal annual accumulation, root turnovers and cycling coefficients were also assessed. S. maritima showed the higher root turnovers and cycling coefficients for most of the analyzed metals, making this a phytostabilizer specie. By contrast the low root turnover, cycling coefficient and low root necromass generation makes S. perennis the most suitable specie for phytoremediation processes. Although the high amounts of metal return to the sediments, due to root senescence, salt marshes can still be considered sinks of heavy metals, cycling heavy metals mostly between sediment and root.     

Precipitation of Zn(II), Cu(II) and Pb(II) at bench-scale using biogenic hydrogen sulfide from the utilization of volatile fatty acids

Biological production of hydrogen sulfide (H(2)S) using sulfate-reducing bacteria (SRB) has important potential within environmental biotechnology. The aim of this work was to study the possibility of using SRB for the treatment of an acid mine drainage (AMD) at bench-scale. This process involved three stages: the optimization of H(2)S production through the utilization of total volatile fatty acids (TVFAs) by SRB, the establishment of a biofilm reactor for sulfide production, and the precipitation of metals by using the biologically produced H(2)S. The substrates used for TVFAs production consisted of papaya, apple and banana. The H(2)S produced from the degradation of TVFAs was utilized for the precipitation of a metal-contaminated effluent collected from Bolivar mine (Oruro, Bolivia). The maximum concentration of H(2)S obtained was approximately 16mM. Removal efficiencies of ca. 100% for copper, above 94% for zinc, and above 92% for lead were achieved.     

Relationship between (210)Pb(ex) activity and sedimentary organic carbon in sediments of 3 Chinese lakes

This report demonstrates that organic matter was an important factor in lake sediment ²¹⁰Pb_ex dating. Sediment cores from lakes in central and western China with different-trophic levels were collected, and the ²¹⁰Pb_ex activity and total organic carbon (TOC) were measured. The Rock-Eval pyrolysis technique was used to deconvolute TOC into free hydrocarbons (S1), thermally less-stable macromolecular organic matter (S2a), kerogen (S2b), and residual carbon (RC). The results show significant correlations between TOC and ²¹⁰Pb_ex, particularly between S2a and ²¹⁰Pb_ex, in all the sediment cores. This indicated that the algal-derived organic component S2a may play the most important role in controlling the distribution of ²¹⁰Pb_ex. Scavenging by algal-derived organic matter may be the main mechanism. As chronology is the key to the understanding of pollution reconstruction and early diagenesis in sediments, more attention should be paid to the influence of organic matter on ²¹⁰Pb_ex.     

Relationship between chromium(VI) resistance and extracellular polymeric substances (EPS) concentration by some cyanobacterial isolates

BACKGROUND, AIM, AND SCOPE: Chromium(VI) resistance and its association with extracellular polymeric substance (EPS) concentration in cyanobacteria was investigated. Increased EPS concentration was associated with Cr(VI) resistance. The most resistant isolate, Chroococcus sp. H(4), secreted the most EPS (427 mg/L). MATERIALS AND METHODS: EPS concentration of the two most resistant isolates (Chroococcus sp. H(4) and Synechocystis sp. S(63)) was investigated following exposure to 15 and 35 ppm Cr(VI). The composition of EPS produced by Chroococcus sp. H(4) following exposure to 10 ppm Cr(VI) was analyzed using high-performance liquid chromatography. Control EPS was composed of glucose (99%) and galactronic acid (1%); in the presence of 10 ppm Cr(VI), EPS composition changed to glucose (9%), xylose (75%), rhamnose (14%), and galacturonic acid (2%). RESULTS AND DISCUSSION: Results indicated that (1) exposure to elevated concentrations of Cr(VI) affected the composition of EPS produced by Chroococcus sp. H(4), and (2) there was a correlation between Cr(VI) resistance and EPS concentration in some cyanobacteria.     

Frequency of hepatocellular fibrillar inclusions in European flounder (Platichthys flesus) from the Douro River estuary,Portugal

Liver lesions in wild fish have been associated with xenobiotic exposure. Facing reports of pollution in the Douro River estuary (north of Portugal), we have been making field surveys using fishes and targeting histopathological biomarkers of exposure and effect. Herein, we intended to better characterize and report the rate of one poorly understood lesion—hepatocellular fibrillar inclusions (HFI)—found in European flounder (Platichthys flesus). With this report, we aimed to establish sound baseline data that could be viewed as a starting point for future biomonitoring, while offering the world's second only pool of field data on such a liver toxicopathic lesion, which could be compared with data available from the UK estuaries. Sampling was done in the Douro River estuary over 1 year. A total of 72 animals were fished with nets, in spring–summer (SS) and autumn–winter (AW) campaigns. Livers were processed for histopathology and both routine and special staining procedures (alcian blue, periodic acid Schiff (PAS), tetrazonium coupling reaction). Immunohistochemistry targeted AE1/AE3 (pan cytokeratins). The severity of the HFI extent was graded using a system with four levels, varying from 0 (absence of HFI) to 3 (high relative density of cells with HFI). Cells (isolated/groups) with HFI appeared in 35 % or more of the fish, in the total samples of each season, and over 40 % in more homogeneous sub-samples. There were no significant differences when comparing samples versus sub-samples or SS versus AW. When merging the data sets from the two seasons, the frequency of fish with HFI was ≈36 % for the total sample and ≈49 % for the sub-sample. The extreme group (biggest and smallest fish) revealed a HFI frequency of only 16 %, which differed significantly from the total and sub-sampled groups. Immunostaining and PAS were negative for the HFI, and alcian blue could, at times, faintly stain the inclusions. These were positive with the tetrazonium reaction. We showed the presence of HFI in European flounder from the Douro River estuary, proving that they are essentially protein in nature, that no seasonal changes existed in the HFI frequency, and that it was rarer in the smallest and biggest fish groups. Within the ranges of weight/size of our total sample, we estimate that the frequency of HFI in the local flounder is ≈35 %. That rate stands as a baseline value for future assessments, namely for biomonitoring purposes targeting correlations with the estuary pollution status.     

Tissues and hair residues and histopathology in wild rats (Rattus rattus L.) and Algerian mice (Mus spretus Lataste) from an abandoned mine area (Southeast Portugal)

Data gathered in this study suggested the exposure of rats and Algerian mice, living in an abandoned mining area, to a mixture of heavy metals. Although similar histopathological features were recorded in the liver and spleen of both species, the Algerian mouse has proved to be the strongest bioaccumulator species. Hair was considered to be a good biological material to monitor environmental contamination of Cr in rats. Significant positive associations were found between the levels of this element in hair/kidney (r=0.826, n=9, p<0.01) and hair/liver (r=0.697, n=9, p=0.037). Although no association was found between the levels of As recorded in the hair and in the organs, the levels of this element recorded in the hair, of both species, were significantly higher in animals captured in the mining area, which met the data from the organs analysed. Nevertheless, more studies will be needed to reduce uncertainty about cause-effect relationships.     

Enzymatic biomarkers in the crab Carcinus maenas from the Minho River estuary (NW Portugal) exposed to zinc and mercury

Zinc and mercury are common contaminants of estuaries and coastal ecosystems where they may induce adverse effects on the biota. Carcinus maenas is a key-species in several European estuaries, living in close association with the sediment where a considerable number of environmental contaminants, including zinc and mercury may accumulate. In the present study, the acute effects of zinc and mercury on C. maenas from the Minho River Estuary (NW Portugal) were investigated by using the activity of the enzymes cholinesterase (ChE), lactate dehydrogenase (LDH) and glutathione S-transferases (GST) as effects' criteria. Crabs were exposed for 96h to several concentrations of Zn(2+) (0, 1.84, 3.71, 7.39 and 14.79mg/l) or Hg(2+) (0, 0.09, 0.19, 0.37 and 0.74mg/l). The choice of Zn(2+) test concentrations was based on the LC50 value (14.86mg/l) determined in a first part of the study, while the choice of Hg(2+) concentrations was based on values from the literature. At the end of the bioassays, eye, muscle and hepatopancreas tissues were isolated and used for ChE, LDH and GST determinations, respectively. Zinc significantly inhibited ChE activity (p<0.05, EC50=14.68mg/l), caused significant alterations of GST activity (p<0.05) and induced LDH activity (p<0.05) at the exposure of 14.79mg/l. Mercury significantly inhibited ChE activity (p<0.001, LOEC=0.09mg/l, EC50=0.235mg/l) and increased both GST (p<0.05, LOEC=0.774mg/l) and LDH activities (p<0.05, LOEC=0.119mg/l). These results suggest that both metals interfere with cholinergic neurotransmission in C. maenas by inhibiting ChE activity. In addition, they also interfere with GST activity and this may reduce the capacity of detoxification of some chemicals and/or to increase the probability of oxidative stress to occur. Furthermore, both metals increase LDH activity, suggesting an interference with energy production pathways. Therefore, the presence of zinc and mercury in estuaries at concentrations in the mg/l or mug/l range, respectively, may have a negative impact on C. maenas.     

Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Relationship between leaf life-span and photosynthetic activity of Quercus ilex in polluted urban areas (Rome)

Anatomical, morphological and physiological leaf traits of Quercus ilex in response to different traffic levels (high traffic level, type A sites; average traffic level, type B sites; control sites, type C sites) were analysed in Rome. Superficial leaf deposits were analysed comparing unwashed and washed leaf samples. Washing lowered Pb 61% in A, 54% in B and 27% in C. Sr, Fe, Cu, Zn and Al showed the same trend as Pb. The higher photosynthetic activity of 1-year-old leaves (Pn=7.0+/-2.9 micromol m(-2 )s(-1), average value) in A sites with respect to B sites (6.7+/-2.4 micromol m(-2 )s(-1)) and C sites (6.7+/-1.8 micromol m(-2 )s(-1)) seems to be related to higher stomatal conductance (g(s)=0.13+/-0.06 mol m(-2 )s(-1)), higher total chlorophyll content (Chl=1.57 mg g(-1)) and higher leaf thickness (L(T)=218.9 microm), particularly palisade parenchyma thickness (109.4 microm). Q. ilex showed, on average, 95% of 1-year-old leaves and rarely 2-year-old leaves in A and B sites; 77% 1-year leaves, 20% previous-year leaves and sporadic 3-year leaves in C sites. The enhanced leaf senescence in A sites is compensated by a stimulated shoot production (18% higher with respect to C sites); 25% increased specific leaf area seems to be compensatory growth occurring in order to increase the size of the assimilatory area. The inverse trend of leaf life-span and Pn seems to be Q. ilex' adaptive strategy in polluted areas.     

Emission profiles of polychlorinated dibenzodioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like PCBs and hexachlorobenzene (HCB) from secondary metallurgy industries in Portugal

This paper reports, for the first time, a study of dioxin emissions from 10 siderurgies and metallurgies, secondary copper, aluminum and lead metallurgies, in Portugal. The study reports the emission factors and total emission amounts of PCDD/Fs, dioxin-like PCBs and hexachlorobenzene (HCB). The congener patterns were characterized and are discussed. The results showed that the total amount of PCDFs is higher than PCDDs in flue gas of each industrial unit. The toxic equivalent emission factors of pollutants emitted are 3098-3338 ngI-TEQt(-1) for PCDD/Fs and 597-659 ng I-TEQt(-1) for dioxin-like PCBs in siderurgies production (total estimated emission amounts released to atmosphere of 3.9-4.5 g I-TEQyr(-1)), 50-152 ng I-TEQt(-1) for PCDD/Fs and 24-121 ng I-TEQt(-1) for dioxin-like PCBs in ferrous foundries production (total estimated emission amounts released to atmosphere of 0.0010-0.0016 g I-TEQyr(-1)) and 5.8-5715 ng I-TEQt(-1) for PCDD/Fs and 0.49-259 ng I-TEQt(-1) for dioxin-like PCBs in non-ferrous foundries production (total estimated emission amounts released to atmosphere of 0.00014-0.12 g I-TEQyr(-1)). The HCB emission from siderurgies production is 0.94-3.2 mg t(-1) (total estimated emission amounts released 0.94-3.8 g yr(-1)), being much smaller, residual, in the emissions of the other types of plants (0.0012-0.026 mg t(-1) production and total estimated emission amounts released to atmosphere of 0.013-1.7 mg yr(-1)).     

Equilibrium partitioning of (14)C-benzo(a)pyrene and (14)C-benazolin between fractionated phases from an arable topsoil

Equilibrium partitioning of hydrophobic (14)C-benzo(a)pyrene and hydrophilic (14)C-benazolin between fractionated phases from an arable topsoil of Merzenhausen (Germany) was investigated. Topsoil samples were collected from lysimeters which were incubated with different residual crops. A physical soil fractionation based on sedimentation and centrifugation steps was performed after water extraction. Four soil phases were obtained designated sediment (SED) phase (>20 microm), microaggregate (MA) phase (2 microm-20 microm), colloid (COL) phase (<2 microm) and electrolyte (EL) phase. The distribution of (14)C-benzo(a)pyrene, (14)C-benazolin and organic carbon between the soil phases was established. Enrichment factors for the two chemicals and organic carbon are higher in the COL and MA phases than in the SED phase. The distribution constant K(d) of chemicals for Merzenhausen topsoil was calculated according to two-phase or three-phase partitioning models. The three-phase partitioning model presumes the contribution of the organic carbon for the binding of chemicals. A log K(oc) of 5.55 can be calculated in the case of (14)C-benzo(a)pyrene, which is typical of the hydrophobic association with the soil organic carbon. In the case of (14)C-benazolin, much higher K(d) and K(oc) values were calculated than found with parent molecules after short-time experiments. Long-term aging processes must be considered. Specific effects on the chemical distribution due to the different crop residues were not detected.     

Relationship between antibiotic residues and occurrence of resistant bacteria in Nile tilapia (Oreochromisniloticus) cultured in cage-farm

The aim of this study was to investigate the relationship between antibiotic residues found in the muscle of cage-farm-raised Nile tilapia (Oreochromisniloticus), the occurrence of resistant bacteria, and the sanitary practices adopted by farmers in Ilha Solteira reservoir, Brazil. Nine fish (three small fish, 40–200 g; three medium-sized fish, 200–500 g; and three large fish, 500–800 g) were collected from four cage farms every three months from April 2013 to January 2014. Ten antibiotic residues were determined using liquid chromatography-mass spectrometry, and bacteria were isolated and tested for antibiotic resistance to determine the multiple antibiotic resistance (MAR) index. Only three antibiotics (oxytetracycline, tetracycline, and florfenicol) were detected in the muscle of Nile tilapia, and their residues were the highest in small fish; however, the MAR index was higher in large fish. In addition, a direct positive relationship between the MAR index and the concentration of antibiotic residues in Nile tilapia was found. Overall, the adoption of prophylactic management practices improved the sanitary status of cage farms, reducing bacterial infections and hampering the development of antibiotic-resistant bacteria.