Environmental fate of pesticides used in Australian viticulture III. Fate of dithianon from vine to wine

Pinot noir, bastardo, rkaziteli and semillon grapes on vines grown in the Barossa Valley of South Australia were treated with a commercial dithianon formulation. The grapes were harvested by hand eight days later, and made into wine. Grab samples of berries, grape juice and the young wine were analysed for fungicide residues. No dithianon was detected in control grape samples, grape juices or wines. Significant dithianon levels were detected on the skins of treated grape samples. Dithianon is stable on the surface of grapes under the ambient conditions prevalent under the grape canopy for at least two weeks. No dithianon was detected in grape juice, on grape skins after berry crushing, in the lees, or in the young wine. Dithianon is unstable in grape juice and wine. Dithianon half‐life (initial concentration = 1 μg/mL) in semillon grape juice = 2.8 h, semillon wine = 0.58 h, pinot noir grape juice = 4.6 h, and pinot‐noir wine = 0.29 h. Treatment with fining agents or heat does not significantly reduce the rate of degradation. These results suggest that spraying table grapes with dithianon two weeks before harvest would result in exposure to essentially the full dose of active ingredient sprayed, and increase the risk to human health through ingestion of this compound. However, any threat to human health from ingestion through grape juice or wine is limited since any contact with grape juice or wine leads to rapid decomposition of dithianon by some as yet undetermined process.     

Persistence of gemfibrozil, naproxen and mefenamic acid in natural waters

The occurrence of pharmaceuticals in natural waters is a potential threat to human nutrition and ecosystem quality. The persistence of the acidic pharmaceuticals gemfibrozil, naproxen and mefenamic acid was studied in surface waters of Maracaibo Lake and Tule reservoir (Venezuela) under laboratory conditions. A quick and easy analytical method was developed for the determination of the acidic drugs at microgram per liter levels using aqueous derivatization, liquid–liquid extraction and gas chromatography–mass spectrometry. Pharmaceuticals degradation followed a pseudo first-order kinetic and their half-lives were calculated for every experimental condition. Under sunlight, naproxen and mefenamic acid were degraded at moderate rates with half-lives from 9.6 ± 0.5 to 27.0 ± 6.6 days, while gemfibrozil had a higher persistence (t _1/2 = 119.5 ± 15.6 − 288.8 ± 61.3 days).     

Application of an inclusion complex for determination of dithianon residues in water and fruits

A 3,3′-benzidine/β-cyclodextrin fluorescence derivative (BCDFD) was prepared and characterized by means of elemental analysis and ¹H NMR. An inclusion complex was formed between BCDFD and the pesticide dithianon based on the internal cavity of β-cyclodextrin (β-CD), and the binding constant (K_S ) of the inclusion complex was investigated. The inclusion complex could be applied for the determination of dithianon residues. Based on this, a sensitive method for the determination of dithianon was established. The linear dynamic range was from 0.63 to 12.5?mg?L^?1 with a correlation coefficient of 0.9927. The limit of detection for an aqueous solution of standard and the relative standard deviation (RSD) were 10.6?µg?L^?1 and 0.76%, respectively. The proposed method has been successfully applied for the determination of dithianon residues in water and fruit samples with satisfactory results, and recoveries in the range of 96.0–108% were obtained. The method is rapid, direct, economical, and sensitive for dithianon analysis.     

Photocatalytic oxidation of humic substances with TiO<Subscript>2</Subscript>-coated glass micro-spheres

The photocatalytic oxidation of humic substances in aqueous solutions and natural waters with TiO₂ attached to buoyant, hollow glass micro-spheres was studied. A maximum oxidation efficiency of 3.6 mg W^–1 h^–1 was achieved in neutral or alkaline media at a plane surface concentration of the catalyst attached to the micro-spheres of 25 g m^–2. Proceeding by different mechanisms in acidic and alkaline media, the photocatalytic oxidation efficiency did not benefit from an excessive presence of hydroxyl radical promoters, hydrogen peroxide and alkali.     

Chemical composition of rivers and streams in the forest and savanna zones of Nigeria

The aim of this study is to investigate the differences in the chemical conditions of lotic waterbodies in the two major ecosystems in Nigeria, the forest and savanna zones. The forest waters were slightly acidic (mean±SD pH = 6.72±0.58) while the savanna waters were slightly alkaline (pH = 7.11±0.33). The cationic order of dominance in the forest waters was Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ in contrast to Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ in savanna waters. The forest waters were chlorided (typical of coastal and/or marine waters) whereas the savanna waters were carbonated in nature, typical of the worldwide freshwater. Organic carbon was significantly higher in forest waters than in the savanna waters (p < 0.05) while nutrient compounds were significantly higher in savanna waters than in forest waters. The seasonal variation of the chemical parameters was generally more evident in savanna than in forest waters. The differences in water quality between the two major vegetation zones reflect the differences in the biogeochemical processes and nutrient cycling that characterise forest and savanna ecosystems.     

Oxidative stress and genotoxicity of 1-methyl-3-octylimidazolium chloride on loach (Misgurnus anguillicaudatus)

This study was a preliminary step to evaluate the acute toxicity of 1-methyl-3-octylimidazolium chloride ([C₈mim]Cl) on loach (Misgurnus anguillicaudatus) by determining the effects on hepatic antioxidant enzyme activities and by the comet assay. The results showed that [C₈mim]Cl had acute toxicity at concentrations above 20 mg L^?1, inducing oxidative stress and genotoxicity on fish liver cells. In respect to enzyme activities, [C₈mim]Cl induced changes in the activities of superoxide dismutase, catalase, and glutathione content the livers of fish exposed at 20–80 mg L^?1. [C₈mim]Cl at the same exposure level caused a remarkable increase in malondialdehyde level. The comet assay indicated that [C₈mim]Cl at 20–80 mg L^?1 induced genotoxicity in liver cells. With increased exposure concentration and time, the two comet parameters trailing rate and tail moment were significantly increased, with significant differences (P < 0.05) observed between control group and each treatment group. The present study shows that ionic liquids can be a threat to the health of aquatic organism when accidentally released to aquatic ecosystems.     

The chemistry of aluminum in the environment

There is increased concern over the effects of elevated concentrations of Al in the environment. Unfortunately, studies of the environmental chemistry and toxicity of Al have been limited by our understanding of the processes regulating the aqueous concentration, speciation and bioavailability of this element.Although Al is the most abundant metallic element in the Earth's crust, it is highly insoluble and generally unavailable to participate in biogeochemical reactions. However, under highly acidic or alkaline conditions, or in the presence of complexing ligands, elevated concentrations may be mobilized to the aquatic environment. Ecologically significant concentrations of Al have been reported in surface waters draining acid-sensitive regions that are receiving elevated inputs of acidic deposition. Acid- sensitive watersheds are characterized by limited release of basic cations (Ca²⁺, Mg²⁺, Na⁺, K⁺) and/or retention of strong acid anions (SO₄ ^2–, NO₃ ^–, Cl^–). Under these conditions inputs of strong acids are not completely neutralized, but rather acidic water is exported from the terrestrial environment. It has been hypothesized that acidic deposition to acid-sensitive watersheds mobilizes Al within the mineral soil, causing elevated concentrations in soil solutions and surface waters. As a result of mineral phase solubility constraints, concentrations of aqueous Al increase exponentially with decreases in pH below 6.0.Monomeric Al occurs as a series of complexes in the aqueous environment, including aquo, OH^–, F^–, SO₄ ^2–, HCO₃ ^– and organic species. Of these aquo, OH^–, F^– and organic complexes are the most significant in natural waters.Elevated concentrations of Al are ecologically significant because: 1) Al is an important pH buffer in acidic waters, regulating the lower limit of pH values following acidification by strong acids; 2) through adsorption and coagulation reactions, Al may alter the cycling and availability of important elements like phosphorus, organic carbon and certain trace metals; 3) Al may serve as a coagulant facilitating the removal of light attenuating materials, thereby increasing the clarity and decreasing the thermal stability of lakes; and 4) Al is potentially toxic to organisms. Better understanding of the chemistry and speciation of Al is essential to assess these effects.     

Sensitized photooxygenation of mononitrophenols in micellar media

The singlet molecular oxygen‐mediated photooxidation of simple nitrophenols was studied in micellar (CTAB) alkaline solutions.

A different behaviour for the values of the overall rate constant (K_t ) and the reactive rate constant (K_t ) in the interaction nitrophenol‐singlet molecular oxygen was observed as a function of surfactant concentration. The former decreases as [CTAB] increases, from values of 1–3 × 10⁹ M^–1 s^–1 in the absence of surfactant to values at least one order of magnitude lower at [CTAB] ～0.1 M. Parallel, k_t remains practically unaffected, in values of the order of 10⁶ — 10⁷ M^–l s^–1, depending on the particular nitrophenol, within the same [CTAB] range. The quantum yield of nitrophenols photooxidation reaches a maximum at [CTAB] ～0.1 M.

The results are discussed in terms of a combination of causes, the polarity of the nitrophenolic microenvironment being the driving effect. The implication of the results on environmental decontamination are also analyzed.     

Effects of pulse current electromagnetic fields on human peripheral lymphocytes

The effects of pulsed current electromagnetic fields (PCEMF) on human peripheral lymphocytes sister chromatid exchanges (SCE), and micronuclei (MN) frequencies were investigated. PCEMF were produced by 8/20 μs pulsed current generation with two model types, a long straight wire and a solenoid. Human peripheral lymphocyte samples were exposed to PCEMF (a pulse per min, and continuing for 1 h). SCE and MN assays were used to evaluate the genotoxic effects. The results indicated that SCE and MN incidences correlated positively with B _m and dB/dt. For the long straight wire model, as B _m reached 8.48 × 10^?2 T and dB/dt = 1.06 × 10⁴ T s^?1, the effect was significant. As B _m reached 1.70 × 10^?1 T and dB/dt = 2.13 × 10⁴ T s^?1, the effect was marked. For the solenoid model, the conditions of significant effect were B _m = 0.264 T and dB/dt = 3.30 × 10³ T s^?1 and B _m = 1.32 T and dB/dt = 1.650 × 10⁴ T s^?1. Data indicated that dB/dt was an important factor in increasing the frequencies of MN and SCE in human peripheral lymphocytes.     

Voltammetric studies of damages in DNA by mutagenic and carcinogenic alkylating chemicals

Voltammetry provides new insights into the effects exerted in vitro by methylation of native DNA. Applying single sweep voltammetry at a stationary mercury electrode the successive steps of the destabilization of alkylated DNA are investigated. The methylation of the nucleic acids is manifested by a specific electrochemical response, due to the 7‐methylguanine, a major product of the methylation of DNA. Short time effects of the methylation include the labilization of 4 to 5 base pairs per methylated guanine base. Furthermore, uncommon protonation properties of the base 7‐methylguanine‐cytosine have been detected. Long term effects of the methylation are ultimately spontaneous hydrolytic strand breaks induced by the prior depurination connected with the release of the 7‐methylguanine from the methylated DNA. A half time t_1/2 of 102 h for the depurination at 37°C has been determined. The depurination and the subsequent strand breaks alter the hydrodynamic properties of the damaged DNA, an effect which can be sensitively followed with voltammetry via the resulting changes in the diffusion coefficient of the damaged biopolymer.     

Organics in wheat and rye straw pulp bleaching and combined mill effluents (II) ecotoxicological screening

Potential environmental effects of the discharge of industrial wastewater from manufacturing of bleached straw pulp have been studied. Bleached neutral sulphite straw pulping results in discharges of both black cooking and spent bleaching liquors. Time proportional samples were taken from the combined bleaching effluent and the combined mill effluent, (i) Mutagenic activity of the two samples in an Ames’ test, and (ii) acute toxicity of the combined mill effluent sample towards the photosynthetic activity of natural marine phytoplankton from the receiving waters were determined. Also, acute toxicity was determined of the slowly biodegradable or persistent organics remaining after aerobic stabilization of the sample towards (ii) photosynthetic activity of natural phytoplankton, (iii) mussels (Mytilus edulis), (iv) eels (Anguilla anguilla) and, (v) crustacean (Nitocra spinipes); and furthermore, (vi) reproduction test of the crustacean and (vii) growth inhibition test of the marine diatom (Phaeodactylum tricornutum) were performed. Mutagenicity emission factors (MEF's) and toxicity emission factors (TEF's) were calculated to classify the effluents. Combined mill effluent sample showed a mutagenic activity per t₉₀ of one fourth the activity of a kraft pulp bleaching effluent, and the inhibition of the photosynthesis of natural phytoplankton was significant up to 2600 times dilution. After aerobic stabilization, inhibition was observed up to 400 times dilution. Other effects of the combined mill effluent sample were only significant below 40 times dilution. The bleaching effluent showed a mutagenic activity per t₉₀ comparable to kraft bleaching effluents. Other effects were only significant below 20 times dilution.     

Hydrogeochemistry of the Coxilha das Lombas Aquifer, Brazil

The hydrogeochemical characterization of Coxilha das Lombas Aquifer, Brazil, was studied. Chemical characteristics from 23 groundwater samples and meteoric waters data from public registers were used. The ionic speciation and mineral dissolution/precipitation was calculated by EQ3/6 package software. The results showed low total dissolved solids (TDS) values and slightly acidic pH. The concentration of most abundant ions usually followed this trend Cl⁻>HCO₃ ⁺>SO₄ ²⁻>Na⁺. The characteristics of groundwaters and the chemistry similarity with the meteoric waters reflect their short residence time, due to high hydraulic conductivity, and low degree of water/rock interactions, due to sands composed mainly of quartz.     

Influence of phytoplankton on complexing capacity of seawater†

Differential Pulse Anodic Stripping Voltammetry (DPASV) was employed to measure Apparent Copper Complexing Capacity (L_t) and Stability Constants (K_s) of related cupric complexes of cell exudates of the phytoplanktonic alga Dunaliella salina. Three natural seawater samples collected 0.1, 2, 5 miles off the Tyrrhenian coast were used as culture medium. The measurements were carried out 1h and 7 days after the inoculum. Furthermore, on one culture the medium was passed through C₁₈‐SEP‐PAK cartridges in order to separate the cell exudates. The results show that Dunaliella salina influences the value of L_t but does not affect the value of K_s . The C₁₈SEP‐PAK retain only 50% of the ligands produced by the cells and capable of complexing copper.     

地质封存CO_2泄漏对蚯蚓的毒性效应

二氧化碳捕集与封存技术(CO_2 capture and storage, CCS)是当前国际上公认的CO_2减排的有效措施,但封存在地下的CO_2仍然因为各种不稳定因素存在泄漏风险,对土壤环境及土壤生态系统产生威胁。选择赤子爱胜蚓为研究对象,通过模拟高浓度CO_2对蚯蚓形态与生理变化的影响,探究CCS泄漏所产生的土壤高浓度CO_2对蚯蚓的毒性效应。研究表明,土壤高浓度CO_2使蚯蚓出现生殖环带肿大、尾部串珠以及断尾等外部形态变化,皮肤和刚毛受到损伤并且表皮发生褶皱等现象;随着CO_2浓度的增加以及暴露时间的延长,蚯蚓的死亡率不断增加,土壤高浓度CO_2对蚯蚓的7 d和14 d半致死浓度分别为26.39%和17.78%;蚯蚓体腔细胞溶酶体中性红保留时间(NRRT)减少。因此,蚯蚓有望作为监测CO_2泄漏的指示生物,NRRT可作为识别CO_2泄漏的敏感指标。     

三氯化铝在酸性环境中对斑马鱼幼鱼运动及学习记忆能力的影响

以斑马鱼胚胎和幼鱼为实验对象,探讨三氯化铝(Al Cl3)在酸性环境中对斑马鱼幼鱼运动能力及学习记忆的影响。将受精后6 h(hours post-fertilization)的斑马鱼胚胎分成2个大组,分别为对照组和三氯化铝组,以观察三氯化铝的毒性作用。每一大组又分为中性(pH7.4)、微酸(pH6.4)和酸性(pH5.4)组,以观察酸性环境分别及与三氯化铝的共同毒性作用。分别采用72 hpf斑马鱼幼鱼机械逃避反射实验、144 hpf斑马鱼幼鱼自发运动、168 hpf单一多次光刺激斑马鱼幼鱼实验等探讨在中性、微酸和酸性环境下暴露铝离子对斑马鱼幼鱼运动能力以及学习记忆的影响。结果显示:与中性环境下的三氯化铝组相比,微酸和酸性环境下的三氯化铝组可以使斑马鱼幼鱼机械逃避次数减少(P0.05),平均速度和移动距离下降(P0.001),斑马鱼幼鱼运动轨迹杂乱无章,自发触壁活动减少;单一多次光刺激实验结果发现,微酸和酸性环境下的三氯化铝组使斑马鱼幼鱼到达平台速度的光照次数显著增加且差异具有统计学意义(P0.001)。以上结果说明,三氯化铝在微酸和酸性环境下,能导致斑马鱼幼鱼运动能力及学习记忆能力下降,并且酸度值越小,对斑马鱼幼鱼运动和学习记忆的影响更显著。酸度值与三氯化铝之间存在协同作用,酸性环境可以使三氯化铝毒性增加。     

Degradation and reduction of acute toxicity of environmentally persistent perfluorooctanoic acid (PFOA) using VUV photolysis and TiO2 photocatalysis in acidic and basic aqueous solutions

Degradation and toxicity reduction of perfluorooctanoic acid (PFOA) were investigated using TiO₂ adsorption, vacuum ultraviolet (VUV) photolysis, and VUV/TiO₂ photocatalysis in acidic and basic aqueous solutions. Chemical analyses of PFOA and its selected by-products and an acute toxicity assessment using the luminescent bacteria Vibrio fischeri (Microtox®) were conducted during and after the various treatment methods. PFOA was found to be best treated by VUV/TiO₂ at pH 4 with HClO₄, as illustrated by the almost complete degradation of PFOA within 360?min and rapid removal of acute microbial toxicity within 60?min. This difference in the efficiency may be attributed to the strong oxidation effectiveness of the radical species generated in acidic media and the electron scavenger effect of the addition of HClO₄ in VUV/TiO₂ photocatalysis. In addition, the proposed method could effectively decompose other perfluorocarboxylic acid (PFCA) species (C₃–C₇ perfluoroalkyl groups) if the initial intermediates formed were longer-chain species that degraded stepwise into shorter-chain compounds by VUV photolysis and VUV/TiO₂ photocatalysis in acidic and basic aqueous solutions.     

Photochemistry of halogenated benzene derivatives. part xii.∗ effects of sodium nitrite on the environmental phototransformation of bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) herbicide in water: The photoincorporation of nitrite ions into bromoxynil

Photoreactions of the herbicide bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) (1) were extensively studied in water containing various concentrations of sodium nitrite with radiation of wavelengths around 313 nm. In the absence of NaNO₂, the quantum yields for the photodecomposition of the herbicide I amounted to 0.054±0.005, while such data was in the range of 0.047 ±0.005 to 0.023 ±0.003 in the presence of 0.5 to 25.0 × 10^‐3 m of the inorganic salt. These quantum yield data for the phototransformation of 1 without and with the presence of sodium nitrite followed the Stern‐Volmer equation. The rates of the photolytic destruction of bromoxynil (1) in water were slower in the presence than in the absence of NaNO₂. For example, the irradiation of the 7.8 x 10^‐6M aqueous solution of 1 in the presence of 10 mM sodium nitrite gave rise to the production of three main photoproducts, viz., 3‐bromo‐4‐hydroxy‐5‐nitrobenzonitrile (2), 4‐hydroxy‐3‐nitrobenzonitrile (3), and an “unidentified photoproduct”; 4. In the case of this photoreaction of compound 1, the percentages of maximum concentration of the photoproducts 2, 3, and 4 were achieved after 14, 44.5, and 60‐min photolyses of 1, respectively; the starting material 1 completely disappeared after 60‐min photolysis. The photoproducts 2 and 3 were identified through the interpretation of the GC‐MS data. Both thhe mass and FT‐IR spectra of the product 4 indicated the possible presence of a COOH group in 4.     

Are barnacle larvae able to escape from the threat of UV?

Earlier laboratory experiments suggested that environmental levels of UV-B radiation can damage the eyes of barnacle naupliar larvae and impair their phototactic behaviors. However, since barnacle larvae may avoid UV by migrating to deeper waters, it is not known whether such impairment would actually occur under field conditions. For the first time, this study provides both field and laboratory evidences to show that prevailing UV-B in the natural habitat of barnacle larvae could be an important environmental factor affecting natural barnacle populations. We here showed that although barnacle nauplii may avoid UV-B irradiation by downward migration, the amount of UV energy (9.8 × 10⁻⁶ J) received by a naupliar eye during downward migration in the natural water column is within the same order of magnitude as the total energy (7.5 × 10⁻⁶ J) sufficient to cause damages to naupliar eye and impair their phototactic responses. It is possible that solar UV-B prevailing at shallow waters would pose a similar threat to other zooplankton species over large geographic scale.     

Microsatellite DNA markers and morphometrics reveal a complex population structure in a merobenthic octopus species (<Emphasis Type="Italic">Octopus maorum</Emphasis>) in south-east Australia and New Zealand

Five polymorphic microsatellite loci were developed and then used to assess the population genetic structure of a commercially harvested merobenthic octopus species (Octopus maorum) in south-east Australian and New Zealand (NZ) waters. Beak and stylet morphometrics were also used to assess population differentiation in conjunction with the genetic data. Genetic variation across all loci and all sampled populations was very high (mean number alleles = 15, mean expected heterozygosity = 0.85). Microsatellites revealed significant genetic structuring (overall F _ST = 0.024, p < 0.001), which did not fit an isolation-by-distance model of population differentiation. Divergence was observed between Australian and NZ populations, between South Australia and north-east Tasmania, and between two relatively proximate Tasmanian sites. South Australian and southern Tasmanian populations were genetically homogeneous, indicating a level of connectivity on a scale of 1,500 km. Morphometric data also indicated significant differences between Australian and NZ populations. The patterns of population structuring identified can be explained largely in relation to regional oceanographic features.     

Effectiveness of emergent and submergent aquatic plants in mitigating a nitrogen–permethrin mixture

Hydraulically connected wetland microcosms (～50?L) in series were used to test the effectiveness of varying combinations of two common aquatic vascular plants, parrot feather (Myriophyllum aquaticum) and cattail (Typha latifolia), for mitigating contamination from a mixture of nitrogen (ammonium nitrate) and permethrin. The upstream series included Myriophyllum only (M) and Typha only (T) while the combination upstream effluent into downstream series included Myriophyllum into Myriophyllum (M?+?M) and Typha into Myriophyllum (T?+?M). During flow, M into M?+?M more efficiently mitigated nitrogen than T into T?+?M. Post-flow, nitrogen removal efficiency was greater for T versus M and M?+?M versus T?+?M. Mean aqueous dissipation half-lives (t_1/2) of NH₄-N and NO₃-N were more rapid in T than M treatments. Ammonium and nitrate t_1/2 was highly correlated with aquatic plant above-ground shoot biomass. Permethrin mitigation efficiencies and t_1/2 were not significantly affected by plant species either singly or in combination. Trans-permethrin t_1/2 was moderately correlated with plant biomass, but not cis-permethrin t_1/2. Results of this study indicate differences in aquatic plant species and flow path influence nitrogen removal but not permethrin. However, plant species appears less important than overall plant biomass in ascertaining aquatic plant effectiveness in mitigating a nitrogen–permethrin mixture.