Identification of highly brominated analogues of Q1 in marine mammals

Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C(9)H(3)N(2)Br(6)Cl, C(9)H(3)N(2)Br(7), and C(9)H(4)N(2)Br(5)Cl. They were identified using high and low resolution gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC suspected to be naturally produced. These compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso's dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 microg/g (lipid weight). The regiospecificity of C(9)H(3)N(2)Br(6)Cl is suggestive of a biogenic origin. Debromination of C(9)H(3)N(2)Br(6)Cl may be significant in the formation of C(9)H(4)N(2)Br(5)Cl.     

Diminution of migration of phthalic acid esters in tequila beverage by the year of production

Abstract

The presence of diethyl-phthalate (DEP), dibutyl-phthalate (DBP), butylbenzyl-phthalate (BBP), diethylhexyl-phthalate (DEHP) and diisononyl-phthalate (DINP) was determined in 295 tequila samples. They were grouped by age of maturation (white, aged, extra aged or ultra aged) and year of production (between 2013 and 2018). Gas Chromatography coupled with Mass Spectrometry was used for identification and quantification. The results showed that 65 samples (22% of the total) were phthalate free. DEP (0.13-0.27?mg/kg), BBP (0.05–2.91?mg/kg) and DINP (1.64–3.43?mg/kg) were detected in 11 (3.73%), 37 (12.54%) and 5 (1.69%) samples, respectively. But, these concentrations did not exceed the maximum permitted limits (MPL) of phthalates for alcoholic beverages. DBP (0.01–2.20?mg/kg) and DEHP (0.03–4.64?mg/kg) were detected in 96 (32.54%) and 224 (75.93%) samples, from them only 10 (3.39%) and 15 (5.08%) samples, respectively, exceeded the MPL for alcoholic beverages and they were few tequilas produced in the year 2014 or before. DEHP was the most frequent phthalate found in tequila and observed DEHP concentrations were 2-times higher in ultra aged tequilas compared to those in white tequilas. We concluded that all tequilas produced in 2015 and after, satisfied the international standards for these compounds.     

Analysis of serpentinophytes from north-east of Portugal for trace metal accumulation--relevance to the management of mine environment

In north–east of Portugal, the serpentinized area is about 8000 ha with a characteristic geology and flora. The serpentine plant community and respective soils were analyzed to examine the trace metal budget in different tissues of the plants exhibiting resistance to trace metals. One hundred and thirty five plant species belonging to 39 families and respective soils have been analyzed for total Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Substantial amounts of Ni, Cr, Co and Mn were detected in plant tissues which are listed below: Ni: Alyssum serpyllifolium (38 105); Bromus hordeaceus (1467); Linaria spartea (492); Plantago radicata (140); Lavandula stoechas (118) and Cistus salvifolius (114); Cr: L. spartea (706.7); Ulmus procera (173.4); A. serpyllifolium (129.3); Cistus ladanifer (40.8); L. stoechas (29.5); P. radicata (27.81); Setariopsis verticillata (25.7); Plantago lanceolata (24); Digitalis purpurea (23.4); Logfia minima (23.1); Arenaria querioides (23); Hieracium peleteranum (22.7); Arenaria montana (14.5); Co: A. serpyllifolium (145.1); L. spartea (63.2); P. radicata (10.4); H. peleteranum (7.3); Lepidium heterophyllum (6.9); A. querioides (6.6); C. salvifolius (6.5); C. ladanifer (6.3); L. stoechas (6.1); Anthyllis lotoides (6.1); L. minima (6.1); Euphorbia falcata (5.7) and B. hordeaceus (5.6); Mn: A. serpyllifolium (830); L. spartea (339); L. stoechas (187.1); L. minima (182.7); Castanea sativa (125); Spergula pentandra (124); P. radicata (119); Cytisus striatus (115.4); Quercus pyrenaica (110); Teucrium scorodonia (109.4); Fraxinus vulgaris (109); Anthyllis sampaiana (108); Quercus ilex (108). The significance of serpentine flora, need for conservation of these fragile and environmentally invaluable plant resources for possible use for in situ remediation of metalliferous substrates are presented in this paper.     

Influence of metal ion on sorption of p-nitrophenol onto sediment in the presence of cetylpyridinium chloride

Heavy metals and surfactants have a significant effect on the sorption of organic contaminants. In this study, batch equilibrium experiments were carried out to investigate the influence of Pb(NO(3))(2) on the sorption of p-nitrophenol (PNP) onto sediments in the presence of cationic surfactant cetylpyridinium chloride (CPC). Results indicated that in the complex system containing PNP, Pb(NO(3))(2) and CPC, the sorption of PNP decreased with increasing concentration of Pb(NO(3))(2) due primarily to competing for adsorption sites. Likewise, partitioning of PNP in adsorbed surfactant layers and micelles decreased with increasing level of Pb(NO(3))(2). Moreover, the influence of different metal ions (Pb(2+), Cd(2+), Zn(2+)) was examined and results indicated that the presence of heavy metals inhibited the sorption of PNP in the order: Pb(2+)>Cd(2+)>Zn(2+). The competitive effect of the heavy metals was in agreement with the hydration energy and hydrated radius. The results are believed to provide a useful insight into describing the transport and fate of PNP in natural environments.     

Investigation of the characteristics of the reflectivity of clouds

This paper investigates some of the reflectivity characteristics that clouds (when modelled as solid bodies) must exhibit to be compatible with observations that the reflecting surface of a cloud (i) appears almost equally bright across its face, (ii) is brightest when the cloud is opposite to the Sun but decreases in brightness as the cloud moves to other positions and (iii) increases in brightness with increasing optical thickness of the cloud in the observer's line of sight. These observations, respectively, are shown to imply that the peak value of the bidirectional total reflectivity from a cloud surface (i) increases in inverse proportion to the cosine of the angle between the Sun and the normal to the cloud surface, as the incident angle increases, (ii) appears to be directed back in the direction of the incident radiation, and (iii) increases as optical thickness of the cloud in the observer's line of sight increases. The results could have application in many fields (e.g. modelling diffuse radiance distributions for cloudy skies).     

The evaluation of stability during the composting of different starting materials: comparison of chemical and biological parameters

Three blends formed by: (i) food processing waste (CP(FP)), (ii) waste water sewage sludge (CP(WW)), and (iii) their mixture (CP(FP+WW)), blended with tree pruning as bulking agent, were composted over 3 months. During composting the blends were monitored for the main physical-chemical characteristics: temperature, oxygen saturation level (O(2)%), pH, total and volatile solids, total organic carbon, and organic nitrogen (N(org)). In addition to the main parameters, the dissolved organic carbon (DOC), the inorganic nitrogen and the Oxygen Uptake Rate (OUR) were monitored. All the mixtures easily reached a peak temperature around 70°C, related to the lowest O(2)%. After 90 d, CP(FP), CP(FP+WW), and CP(WW) showed an organic matter mineralization of 43%, 35% and 33%, respectively; CP(FP) fitted an exponential model while both CP(FP+WW), and CP(WW) fitted a logistic model. During composting an OUR reduction of 79%, 78% and 73% was registered in CP(FP), CP(FP+WW), and CP(WW), respectively; the OUR successfully fitted the adopted exponential model and well reflected the stabilization process in time. The N(org) recovery at the end of the process was positive only in CP(WW) (11.6%). The DOC significantly decreased during the composting process but did not successfully fit any model. The mineral nitrogen did not follow the typical pattern with NH(4)(+) disappearance and NO(3)(-) accumulation. Strong NO(3)(-) losses were evident in all blends, while NH(4)(+) accumulations were detectable only in CP(FP), and CP(FP+WW). The NH(4)(+)/NO(3)(-) ratio did not satisfactorily reflect the composting process over time. The comparison of the first order (exponential) and logistic (sigmoidal) models applied to the OUR and OM course highlights the role of mineral nitrogen as limiting factor during composting of the more stabilized sludge.     

Estrogenic and thyroid hormone activity of a series of hydroxy-polychlorinated biphenyls

A series of novel synthetic monohydroxy polychlorinated biphenyls (OH-PCBs) (5 trichloro-, 5 tetrachloro- and 5 pentachloro-compounds) have been characterized (1H and 13C NMR and high resolution MS) and their estrogenic and thyroid hormone activities assessed using a yeast two-hybrid assay, both with and without possible metabolic activation by rat liver S9 preparation. Moderate estrogenic activity was found for 2,3,4(')-trichlorobiphenyl-4-ol (compound 5) but this was eliminated when exposed to the S9 mix. 2,2('),3('),4,6-Pentachlorobiphenyl-3-ol (13) and 2('),3,3('),6-tetrachlorobiphenyl-4-ol (10) both showed weak estrogenicity in the absence of the S9 mix. The estrogenicity of compound (10) was enhanced 10-fold by exposure to S9 metabolic activation but that of compound (13) remained unchanged. 2('),4,5('),6-Tetrachlorobiphenyl-2-ol (6) showed strong thyroid hormonal activity (5% of that of T4) whereas 3('),4,6-trichlorobiphenyl-3-ol (4), compound (10) and 2,3('),4,5('),6-pentachlorobiphenyl-3-ol (14) showed moderate activity, and 2('),3,3('),5-tetrachlorobiphenyl-2-ol (8) and 3,3('),5,5('),6-pentachlorobiphenyl-2-ol (11) showed weak activity. The activity of (4) was eliminated by S9 metabolic activation whereas those of (6) and (14) were weakened and that of (10) remained unchanged.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH(-) . pH(-1). The sediments were spiked with atrazine at 7.25-36.23 mg kg(-1) (6.21 x 10(-7)-3.09 x 10(-6) mol atrazine . g(-1) sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 x 10(-2)-7.04 x 10(-2) d(-1) for the atrazine-spiked sediments.     

Effect of pencycuron on microbial parameters of waterlogged soil

A laboratory study was conducted to monitor the effect of pencycuron [1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea] on microbial parameters of alluvial (AL) soil (Typic udifluvent) and coastal saline (CS) soil (Typic endoaquept) under waterlogged condition. Pencycuron at field rate (FR), 2FR and 10FR affected the microbial biomass C (MBC), soil ergosterol content and fluorescein diacetate hydrolyzing activity (FDHA) differentially. The DCM amendment did not seem to have any counteractive effect on the toxicity of pencycuron on the microbial variables. The change in microbial metabolic quotient (qCO2) and microbial respiration quotient (QR), indicated pencycuron induced disturbance at 10FR. Present study revealed that the metabolically activated microbial population was more suppressed compared to the dormant population.     

Mechanisms of biodegradation of dibenzoate plasticizers

Biodegradation mechanisms were elucidated for three dibenzoate plasticizers: diethylene glycol dibenzoate (D(EG)DB), dipropylene glycol dibenzoate (D(PG)DB), both of which are commercially available, and 1,6-hexanediol dibenzoate, a potential green plasticizer. Degradation studies were done using Rhodococcus rhodochrous in the presence of pure alkanes as a co-substrate. As expected, the first degradation step for all of these systems was the hydrolysis of one ester bond with the release of benzoic acid and a monoester. Subsequent biodegradation of the monobenzoates of diethylene glycol (D(EG)MB) and dipropylene glycol (D(PG)MB) was very slow, leading to significant accumulation of these monoesters. In contrast, 1,6-hexanediol monobenzoate was quickly degraded and characterization of the metabolites indicated that the biodegradation proceeded by way of the oxidation of the alcohol group to generate 6-(benzoyloxy) hexanoic acid followed by β-oxidation steps. This pathway was blocked for D(EG)MB and D(PG)MB by the presence of an ether function.The use of a pure hydrocarbon as a co-substrate resulted in the formation of another class of metabolites; namely the esters of the alcohols formed by the oxidation of the alkanes and the benzoic acid released by hydrolysis of the original diesters. These metabolites were biodegraded without the accumulation of any intermediates.     

Temperature dependence of Henry's law constants of metolachlor and diazinon

A dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube has been used to determine experimentally the Henry's law constants (HLC) of two pesticides: metolachlor and diazinon. The measurements were conducted over the temperature range 283-301 K. At 293 K, HLCs values are (42.6+/-2.8) x 10(3) (in units of M atm(-1)) for metolachlor and (3.0+/-0.3)x10(3) for diazinon. The obtained data were used to derive the following Arrhenius expressions: HLC=(3.0+/-0.4) x 10(-11) exp((10,200+/-1,000)/T) for metolachlor and (7.2+/-0.5) x 10(-15) exp((11,900+/-700)/T) for diazinon. At a cumulus cloud temperature of 283 K, the fractions of metolachlor and diazinon in the atmospheric aqueous phase are about 57% and 11% respectively. In order to evaluate the impact of a cloud on the atmospheric chemistry of both studied pesticides, we compare also their atmospheric lifetimes under clear sky (tau(gas)), and cloudy conditions (tau(multiphase)). The calculated multiphase lifetimes (in units of hours) are significantly lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): metolachlor, 0.4 (2.9); diazinon, 1.9 (5.0).     

Toxic effects of low concentrations of Cu on nodulation of cowpea (Vigna unguiculata)

Although Cu is phytotoxic at Cu(2+) activities as low as 1-2 microM, the effect of Cu(2+) on the nodulation of legumes has received little attention. The effect of Cu(2+) on nodulation of cowpea (Vigna unguiculata (L.) Walp. cv. Caloona) was examined in a dilute solution culture system utilising a cation exchange resin to buffer solution Cu(2+). The nodulation process was more sensitive to increasing Cu(2+) activities than both shoot and root growth; whilst a Cu(2+) activity of 1.0 microM corresponded to a 10% reduction in the relative yield of the shoots and roots, a Cu(2+) activity of 0.2 microM corresponded to a 10% reduction in nodulation. This reduction in nodulation with increasing Cu(2+) activity was associated with an inhibition of root hair formation in treatments containing > or =0.77 microM Cu(2+), rather than to a reduction in the size of the Rhizobium population.     

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).     

Characterization of demethylation of methylmercury in cultured astrocytes

Mercury (Hg) is a well-known neurotoxicant but its toxicity depends on the species present. A steady emergence of inorganic Hg in the brain following chronic and accidental exposure to methylmercury (MeHg) has suggested that MeHg can undergo demethylation. The objective of this study is to develop an in vitro model to study factors affecting Hg demethylation in the central nervous system. Astrocytes obtained from neonatal rat pups were cultured for 24h with 1 microM MeHg in the presence of two pro-oxidants, buthionine sulphoximine (BSO) and rotenone. The BSO treatment produced a 21% increase in reactive oxygen species (ROS) content compared to the control (control vs. BSO; 100+/-1.35 vs. 121+/-1.52 relative fluorescence units (RFU)mg(-1) protein, p<0.001) but did not affect total Hg accumulation (control vs. BSO=86.5+/-4.14 ng mg(-1) vs. 95.7+/-9.26 ng mg(-1)). Rotenone increased ROS levels 107% (control vs. rotenone; 100%+/-1.35 vs. 207%+/-6.78RFU mg(-1)protein, p<0.001) and significantly increased the accumulation of total Hg (control vs. rotenone=86.5+/-4.14 ng mg(-1) vs. 124+/-3.80 ng mg(-1), p<0.001). There was no detectable demethylation in the control or BSO treated group, however, the rotenone treatment significantly increased the demethylation (control vs. rotenone=-1.86+/-5.57% vs. 16.3+/-2.68%, p<0.05). For the first time, we have demonstrated in an in vitro primary astrocyte culture model that MeHg can be converted to inorganic Hg and demethylation increases with oxidative stress. Our results provide a useful model to study demethylation of Hg in astrocytes and to explore potential ways to protect against Hg toxicity.     

Visualisation of the complexity of EUSES

The interdependencies of parameters applied in the models of EUSES are visualised in a directed connectivity graph. The parameters (inputs, defaults, state variables, outputs) are represented by boxes (nodes) and their relations by lines (edges). The visualisation, on the one hand, clarifies the complexity of the models in EUSES and, on the other hand, creates an overview and transparency. The parameters’ relations to each other can be recognised faster, and the models can be better understood. The complexity was quantified by the number (variety), kind (substance parameter, physico-chemical parameter, concentration, other parameters), and depth (dimension) of the parameter and the number of relations (connectivity). The variety of EUSES (without the modelsSimple Treat andSimple Box whose interior structure is not documented and without the effect and risk characterisation) amounts to 466, the connectivity to 961, and the maximal dimension is 21.     

Study of inclusion complex of beta-cyclodextrin and nitrobenzene

beta-cyclodextrin can react with nitrobenzene to form an inclusion complex which is characterized by (1)H NMR and powder X-ray diffractometry. The ratio of beta-CD to NB in inclusion complex is determined as 1:1. At 25 degrees C, the dissociated constant, K(D), of the inclusion complex is measured as 6.5 x 10(-3) M in neutral solution (pH=7.0), but in alkali (pH=13.5), K(D) is 3.2 x 10(-2) M which is much larger than that measured in neutral.     

Investigations of chemical fraction of Co and Ni in industrial fly ash and mobility of metals in environmental conditions

The quantitative evaluation of chemical fraction of Co and Ni in the industrial fly ash by methods of five step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH=7), (ii) acid-soluble (pH=5), (iii) oxide, (iv) sulfide and (v) residue metal fractions. It was discovered, that the total extraction of the studied metals from fly ash to solutions take place in the following quantities Co - 35.5 and Ni - 153.0mgkg(-1). The investigations of chemical fractions proved that the subject metals occur mainly in fly ash as: oxide (Co - 7.0, Ni - 28.5mgkg(-1)) and residue (Co - 11.5, Ni - 42.5mgkg(-1)) as well as sulfide (Co - 8.5, Ni - 46.5mgkg(-1)). Low concentrations of metals for water-soluble fraction (Co - 0.7, Ni - 1.2mgkg(-1)) and acid-soluble fraction (Co - 4.5, Ni - 23.5mgkg(-1)) were observed. The fractions of Co and Ni leachable from the ash in environmental conditions contain: 24.0% (Co) and 23.3% (Ni) of metal total amount in the industrial fly ash. The obtained mobility parameter of Co and Ni can be applied to estimate the concentration increase of mobile and hardly mobile forms of these metals in soil polluted with the ash.     

Development of a multi-factor model for predicting the effects of ambient ozone on the biomass of white clover

Results are presented from the UN/ECE ICP Vegetation (International Cooperative Programme on effects of air pollution on natural vegetation and crops) experiments in which ozone(O(3))-resistant (NC-R) and -sensitive (NC-S) clones of white clover (Trifolium repens cv. Regal) were exposed to ambient O(3) episodes at 14 sites in eight European countries in 1996, 1997 and 1998. The plants were grown according to a standard protocol, and the forage was harvested every 28 days for 4-5 months per year by excision 7 cm above the soil surface. Biomass ratio (NC-S/NC-R) was related to the climatic and pollutant conditions at each site using multiple linear regression (MLR) and artificial neural networks (ANNs). Twenty-one input parameters [e.g. AOT40, 7-h mean O(3) concentration, daylight vapour pressure deficit (VPD), daily maximum temperature] were considered individually and in combination with the aim of developing a model with high r(2) and simple structure that could be used to predict biomass change in white clover. MLR models were generally more complex, and performed less well for unseen data than non-linear ANN models. The ANN model with the best performance had five inputs with an r(2) value of 0.84 for the training data, and 0.71 for previously unseen data. Two inputs to the model described the O(3) conditions (AOT40 and 24-h mean for O(3)), two described temperature (daylight mean and 24-h mean temperature), and the fifth input appeared to be differentiating between semi-urban and rural sites (NO concentration at 17:00). Neither VPD nor harvest interval was an important component of the model. The model predicted that a 5% reduction in biomass ratio was associated with AOT40s in the range 0.9-1.7 ppm x h (microl l(-1) h) accumulated over 28 days, with plants being most sensitive in conditions of low NO(x), medium-range temperature, and high 24-h mean O(3) concentration.     

Accumulation of nutrients in soils affected by perennial colonies of piscivorous birds with reference to biogeochemical cycles of elements

The accumulation of selected N, K, and P forms in soils within three perennial colonies of black cormorant (Phalacrocorax carbo sinensis) and grey heron (Ardea cinerea) located in northern and eastern Poland were investigated. Soil samples were collected beneath the nests from the most representative for each colony plots. Control samples were taken outside the colonies within sites adjacent to the nesting areas but not affected by bird excrement. From each genetic horizon (20 horizons) in soil profiles, a cumulative sample of about 25-30 kg of soil was taken for analysis. Nitrogen by Kjeldahl, ammonium ions (N(NH(4))), nitrates (N(NO(3))), exchangeable potassium (K(ex)), available potassium (K(av)), and available phosphorus (P(av)) were determined. The soils affected by birds demonstrated a very strong enrichment with N, K, and P in comparison to the control sites, especially in the topsoil horizons. The content of N(NH(4)) in individual soil horizons from the colonies was from 1.7 to 10.1 times higher than the respective control, N(NO(3)) from 2.9 to 215.7, K(ex) from 2.0 to 35.1, K(av) from 1.1 to 48.1, and P(av) in the range from 2.4 to 53.0 times. The highest increment of chemical elements was noticeable in the soils of territories inhabited by cormorants and the least in forest occupied by herons. Some relationships between soil texture and accumulation of biogenic nutrients were determined. Clay loam soil showed the greatest enrichment with analysed forms of elements with the exception of N(NH(4)).