Effect of chlorophenolic pesticides on the photochemistry of riboflavin

The possibility of riboflavin sensitized photo‐oxidation of polychlorinated pesticides was investigated. The dye proved to be an inefficient sensitizer for that purpose, when irradiated with visible light, in aereated aqueous solutions. A quenching of singlet and triplet excited states of the chromophore (depending on the concentrations of the quencher) is responsible for this failure in the photo‐degradation of the pesticides, which resulted easily oxidizable, via singlet oxygen mechanism, when proflavine was employed as a sensitizer. Parallel, and as a direct consequence, the rate of aerobic riboflavin photobleaching decreased drastically in the presence of the chlorophenols.

The implication of our results on the inhibition of riboflavin degradation by the presence of chlorinated phenolic pesticides in the environment, is discussed, from the point of view of a kinetic and mechanistic study.     

Mutagenicity of polyaromatic hydrocarbons by chemical models for cytochrome P450 in Ames assay

DNA damage is an important step in carcinogenesis. The Ames assay is a short-term screening of carcinogens that induce DNA damage. Most carcinogens require enzymatic activation through oxidation by cytochrome P450 (CYP450) in the presence of S9 mix. A combination of iron (Fe)(III) porphyrin and an oxidant is also able to oxidize compounds as an alternative metabolic pathway to CYP450. Previously it was reported that a chemical model containing a water-soluble 5,10,15,20-tetrakis(1-methylpyridinium4-yl)porphyrinatoiron(III) chloride (4-MPy) and tert-butyl hydroperoxide (t-BuOOH) activated aromatic amines and amides. In this study, a chemical model composed of an Fe porphyrin, water-insoluble 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatoiron(III) chloride (F₅P) or water-soluble 4-MPy was optimized with an oxidant – t-BuOOH, magnesium monoperoxyphthalate (MPPT), or iodosylbenzene (PhIO). Subsequently the mutagenicity of benzo[a]pyrene (B[a]P) and chrysene in Salmonella typhimurium TA strains was compared. B[a]P was activated by a combination of F₅P or 4-MPy plus MPPT or PhIO in S. typhimurium TA1538. The B[a]P-induced mutagenicity with F₅P plus oxidant was higher than 4-MPy plus oxidant. Mutagenicity of chrysene, a tetracyclic aromatic hydrocarbon, was not detected in the presence of F₅P/PhIO in S. typhimurium TA98, but was activated in the presence of F₅P/MPPT. The F₅P/MPPT activated other polyaromatic hydrocarbons (PAH) in the S. typhimurium TA98 assay including dibenz[a,c]anthracene, dibenz[a,h]anthracene, 3-methylcholanthrene, and benzo[a]anthracene. The results indicated that the F₅P/MPPT was the most efficient model for detecting PAH-induced mutagenicity in the Ames assay.     

Influence of varying nutrient and pesticide mixtures on abatement efficiency using a vegetated free water surface constructed wetland mesocosm

The nutrient and pesticide abatement efficiency of varying mixtures was examined in a vegetated free water surface constructed wetland. Three different agricultural chemical pollutant mixture conditions were assessed: nutrients only (N and P); pesticides only (atrazine, S-metolachlor and permethrin); and a mixture of nutrients and pesticides. With nutrients only, 672 h nutrient mitigation of 77–91% total phosphorous (TP) and 74–98% total nitrogen (TN) was associated with distance from the injection point and rainfall, whereas with nutrient and pesticide mixtures, 672 h nutrient mitigation of 11–71% TP and 84–98% TN were associated with distance and time. With pesticides only, 672 h pesticide mitigation of 50–99% was associated with distance and time, whereas with nutrients and pesticide mixtures, 672 h pesticide mitigation of 48–99% was associated primarily with distance. Dissipation half-lives were 2–10 times greater for P and 1.5–5 times greater for N when pesticides were present. Pesticide dissipation half-lives showed no clear differences with or without nutrients. While vegetated free water surface constructed wetlands can be effective best management practice tools to trap and abate agricultural run-off during rainfall events, efficiencies can be affected by different types of complex pollutant mixtures and wetland design and implementation should accommodate varying efficiencies.     

图像处理在弹琴蛙(Rana adenopleura)蝌蚪生物监测研究中的应用

利用图像处理方法对不同质量浓度的阿特拉津溶液(1mg／L、5mg／L、10mg／L、15me／L)中弹琴蛙(Rana ade-nopleura)蝌蚪行为进行了图像的识别及分析．根据实验结果，利用MATLAB语言编写了弹琴蛙蝌蚪在水族缸中具体分布型判定的程序，采用了负二项分布的参数κ值来反应不同溶液中蝌蚪聚集程度的差异，并作为该指示生物监测阿特拉津水体污染情况的一个指标．结果显示，该程序可如实反映不同污染水体中蝌蚪的聚集程度：经χ^2检验各种水体中蝌蚪均符合负二项分布，同时阿特拉津溶液中蝌蚪的κ值均小于空白对照和丙酮对照，表明阿特拉津溶液的浓度和蝌蚪的聚集程度相关．图9表1参14     

狼尾草根系对阿特拉津长期胁迫的氧化应激响应

通过盆栽实验研究了抗性植物狼尾草根部丙二醛(MDA)、脯氨酸(Pro)、抗坏血酸(As A)含量及超氧化物歧化酶(SOD)、谷胱甘肽还原酶(GR)等氧化应激生理指标对不同浓度阿特拉津长期(48 d)胁迫的响应规律。结果表明:当阿特拉津胁迫浓度分别高于20 mg·kg~(-1)和50 mg·kg~(-1)时,狼尾草根系的MDA与Pro含量较对照组显著升高(P0.05);随着阿特拉津胁迫浓度的增加,狼尾草根部SOD和GR活性呈先升高后降低的趋势,其中当阿特拉津胁迫浓度为20 mg·kg~(-1)时,SOD和GR活性达到最大值;供试植物根系中As A含量与阿特拉津胁迫浓度呈正相关。综上,中低浓度(≤20 mg·kg~(-1))阿特拉津处理没有对狼尾草的根系产生明显的氧化胁迫效应,狼尾草根系的上述抗氧化应激生理指标对于发挥阿特拉津抗性起着重要的作用。     

Effect of short-term atrazine addition on the performance of an anaerobic/anoxic/oxic process

In this study, an anaerobic/anoxic/oxic (A²O) wastewater treatment process was implemented to treat domestic wastewater with short-term atrazine addition. The results provided an evaluation on the effects of an accidental pollution on the operation of a wastewater treatment plant (WWTP) in relation to Chemical Oxygen Demand (COD) and biological nutrient removal. Domestic wastewater with atrazine addition in 3 continuous days was treated when steady biological nutrient removal was achieved in the A²O process. The concentrations of atrazine were 15, 10, and 5 mg·L^?1 on days 1, 2 and 3, respectively. The results showed that atrazine addition did not affect the removal of COD. The specific NH₄ ⁺ oxidation rate and NO₃ ^? reduction rate decreased slightly due to the short-term atrazine addition. However, it did not affect the nitrogen removal due to the high nitrification and denitrification capacity of the system. Total nitrogen (TN) removal was steady, and more than 70% was removed during the period studied. The phosphorus removal rate was not affected by the short-term addition of atrazine under the applied experimental conditions. However, more poly-hydroxy-alkanoate (PHA) was generated and utilized during atrazine addition. The results of the oxygen uptake rate (OUR) showed that the respiration of nitrifiers decreased significantly, while the activity of carbon utilizers had no obvious change with the atrazine addition. Atrazine was not removed with the A²O process, even via absorption by the activated sludge in the process of the short-term addition of atrazine.     

In vitro degradation of the herbicide atrazine by soil and wood decay fungi controlled through Elisa technique

The interaction between atrazine, a triazine herbicide, and a series of decay fungi was characterized in terms of biodegradation of the herbicide and its influence on fungal growth. The following fungi were studied: thermophilic cellulolytic (Penicillium sp. 13) and noncellulolytic (Humicola lanuginosa sp. 5 and 12) strains isolated from self‐heated plant composts, mesophilic diphenol oxidase producing strain Mycelia sterilia INBI 2–26, white‐rot fungi Cerrena maxima, Coriolopsis fulvocinerea and Coriolus hirsutus. Competitive enzyme immunoassay was elaborated for detection of atrazine in cultural liquid. During agar plate cultivation the growth of Humicola sp. 5 was promoted by atrazine whereas the growth of Humicola sp. 12 and Penicillium sp. 13 was suppressed whereas M. sterilia INBI 2–26 was not affected by the herbicide. Neither atrazine‐accelerated nor atrazine‐depressed thermophilic strains decomposed atrazine during 21‐day cultivation according to ELISA data. In contrast, white‐rot fungi Coriolus hirsutus, Coriolopsis fuhocinerea and Cerrena maxima degraded nearly 50% of the herbicide in 5‐day submerged cultivation and 80–92% of the herbicide up to the 40th day. The soil strain M. sterilia INBI 2–26 decomposed 70% of atrazine in 17‐day cultivation. The degradation level depended of the time of atrazine introduction to the growing media. The relationships between the degree of atrazine decomposition and laccase and Mn‐peroxidase production were shown.     

Sediment quality assessment of Beasley Lake: bioaccumulation and effects of pesticides in Hyalella azteca

Beasley Lake is a Conservation Effects Assessment Program (CEAP) watershed in the intensively cultivated Mississippi Delta, USA. Lake sediment quality at three sites was evaluated in 2004 and 2008 for biological impairment and uptake (animal tissue pesticide residues) from 14 pesticides and three metabolites using Hyalella azteca (Saussure). Eleven pesticides and three metabolites were detected in sediment among the three sites in 2004 and all 17 compounds examined were detected among the three sites in 2008, with the herbicide atrazine having the greatest concentrations. Twenty-eight-day H. azteca survival and growth (mg w/w) indicated no survival effects at any site for either year, but growth impairment occurred in H. azteca exposed to sediments in 2004, whereas growth enhancement occurred in H. azteca exposed to sediments at one site in 2008. Pesticides observed in animal tissue pesticide residues occurred more frequently and in greater concentrations in 2004 compared with 2008. Thirteen pesticides were detected in animal tissue pesticide residues in 2004, with chlorpyrifos occurring in the greatest concentrations, and six pesticides were detected in 2008, with p,p′-DDT occurring in the greatest concentrations. H. azteca tissue pesticide residues of seven pesticides, two herbicides, three insecticides, one insecticide metabolite, and p,p′-DDT, were associated with growth.     

Isolation and characterization of an Arthrobacter sp. strain HB-5 that transforms atrazine

A bacterial strain (HB-5) capable of utilizing atrazine as sole carbon and nitrogen source for growth was isolated from an industrial wastewater sample by enrichment culture. The isolate was identified as Arthrobacter sp. according to its phenotypic features, physiologic and biochemical characteristics, and phylogenetic analysis. The strain exhibited faster atrazine degradation rates in atrazine-containing mineral media than the well-characterized atrazine-degrading bacteria Pseudomonas sp. ADP. The broad optimum pH and temperature ranges observed for strain HB-5 indicate that it has potential for remediation of atrazine-contaminated sites. Strain HB-5 first metabolizes atrazine to yield hydroxyatrazine. Then, the bacterium metabolizes hydroxyatrazine to cyanuric acid, but could not mineralize atrazine.     

Degradation of pentachlorophenol in a contaminated soil suspension using hybrid catalysts prepared via urea�Cformaldehyde polycondensation between iron(III)-tetrakis(p-hydroxyphenyl)porphyrin and humic acid

Hybrid catalysts were synthesized by attaching iron(III)-tetrakis(p-hydroxyphenyl)porphyrin (FeTPP(OH)₄) to humic acid (HA) via urea–formaldehyde polycondensation. FTIR spectra of the prepared catalysts indicated that the catalysts prepared via urea–formaldehyde polycondensation contained cross-links between the phenolic groups of FeTPP(OH)₄ and HA, which contains aliphatic amine functional groups. The prepared catalysts were examined for their ability to catalyze the oxidative degradation of pentachlorophenol (PCP) in a contaminated soil suspension. The levels of PCP degradation and dechlorination for the hybrid catalysts were significantly higher than those for the non-modified catalyst, FeTPP(OH)₄.     

Respiratory responses of the estuarine mysid Neomysis integer (Peracarida: Mysidacea) in relation to a variable environment

The euryhaline mysid Neomysis integer (Peracarida: Mysidacea) is a common member of the hyperbenthos of the upper reaches of European estuaries. In the East Looe River Estuary (Cornwall, England), this species experiences extensive tidal and seasonal changes in temperature (3 to 15 °C) and salinity (1 to 34‰). In this investigation, the effects of temperature (5, 10 and 15 °C) and salinity (1, 10, 20 and 30‰) on the oxygen consumption of male and female N. integer are reported, and are related to field measurements to identify the adaptive responses of the respiratory physiology to such a variable environment. The general responses were similar for each sex; however, at any given temperature/salinity combination, male N. integer consumed more oxygen than females. The general trends were increased oxygen consumption with increasing temperature (Q₁₀ values ranged from ∼1.7 to 2.5) and decreased oxygen consumption with increasing salinity. Temperature and salinity interacted at high water antagonistically to minimise changes in mysid oxygen-consumption. When related to tidal fluctuations in temperature and salinity experienced by N. integer inhabiting the East Looe River Estuary, the results reveal how the respiratory physiology of this species is adapted to its variable environment. Received: 16 June 1998 / Accepted: 15 December 1998     

Estimating the uncertainty of pesticide residue analysis from mango using multi-residue analysis and validation of method

Validation of method was performed for various pesticides on mango matrix involving the processing of sample at ambient and cryogenic conditions. The linearity, limits of detection, repeatability, matrix effect, and recovery were studied as the aspects of method validation. The effect of matrix on recovery was found to be medium (20–50%) and strong (>50%). After correction by matrix-matched calibration curves, the recovery was calculated to be in the range of 80–107% and 80–105% at ambient and cryogenic processing, respectively. The precision estimated for the recovery of pesticides obtained from both solvent- and matrix-matched calibration curves and at both the processing conditions was determined to be >20% except for chlorpyrifos and atrazine. The uncertainty established for the methodology was >20%, which substantiates the efficiency and reliability of methodology used for pesticide residue analysis in mango in this study.     

Effects of salinity on endogenous rhythm of the Manila clam, Ruditapes philippinarum (Bivalvia: Veneridae)

The Manila clam Ruditapes philippinarum, an intertidal bivalve, was exposed to different salinity regimes (from 31.0–31.7‰ down to 20‰, 15‰, 10‰, 5‰), and the endogenous rhythm in its oxygen consumption was studied using an automatic intermittent-flow respirometer. When exposed to salinities reduced from 31.5‰ to 20‰ and 15‰ under otherwise constant conditions, the clams recovered a clear endogenous circatidal rhythm in their oxygen-consumption rate after having dampened periods of 12 h and 48 h, respectively. At salinities less than 10‰, however, the oxygen-consumption rate was depressed greatly at the beginning of the experiment for about 36 h and then increased to a level higher than normal, but the rhythm of oxygen consumption was not recovered. The results of this study indicate that the Manila clam, a euryhaline organism, cannot maintain a normal metabolic activity at a salinity lower than 15‰. All clams were dead after exposure at a salinity of 5‰ for 7 days. Received: 28 February 2000 / Accepted: 26 August 2000     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.     

Atrazin

Atmospheric occurrence and deposition of atrazine are measured. During the application of atrazine, highest concentrations reached 1.6 μg·1^?1 in liquid water of lowlying clouds touching mountain tops. Atmospheric deposition, however, hardly amounts to 0.4% of the flux on crop land by direct spraying. Airborne concentrations ranged from less than 0.005 ng·m^?3 to 0.32 ng·m^?3. Contrary to theoretical expectations, almost all atrazine was found in the particulate matter, indicating nonequilibrium with the gas phase. This may inhibit a rapid photochemical decomposition. Human health concerns and environmental risks due to the atmospheric occurrence and deposition of atrazine are judged as minor. This conclusion can be applied to many other, physicochemically related pesticides.     

Modeling the binding of triazine herbicides to humic substances using capillary electrophoresis

The binding of 4 s-triazines herbicides and metabolites, ameline, hydroxyatrazine, atraton, and ametryn to 12 structurally different humic substances was studied by affinity capillary electrophoresis. Binding data were confronted to the structural data of humic acids obtained from spectrometric measurements (UV-Vis, FT/IR, NMR), elemental analysis and potentiometric titration. The results obtained with principal component analysis and partial least square analysis clearly show the importance of carboxylic acidity and aromaticity of the humic ligands in relation to the partial positive charge and relative hydrophobicity of the pesticides.     

Polychaetes associated to a<Emphasis Type="Italic"> Cymodocea nodosa</Emphasis> meadow in the Canary Islands: assemblage structure,temporal variability and vertical distribution compared to other Mediterranean seagrass meadows

The structure, diversity and temporal distribution of the infaunal polychaetes associated with Cymodocea nodosa meadows were studied in Tenerife (Canary Islands). The samples were collected monthly throughout a year, to depths of 13–16 m. The sediment was extracted by means of PVC cores, in which four layers were separated (i.e. 0–5 cm, 5–10 cm, 10–20 cm and 20–30 cm). A total of 1,167 polychaete specimens, belonging to 69 taxa were collected, representing one of the most dominant groups in the benthic assemblage throughout the entire year. The most common families were Syllidae, Paraonidae and Spionidae, both in terms of abundance and species richness. The dominant species were Streptosyllis bidentata, Aricidea assimilis and Exogone parahomoseta mediterranea, representing also the only constant species throughout the year. The highest values of species richness, diversity, equitability and abundance of polychaetes occurred in September. The multifactorial analysis of abundances (i.e. cluster analysis and non-metric, multi-dimensional scaling) indicated temporal segregation of the samples from July, August and September (i.e. the warmest months) with respect to those from the rest of the year, due to structural differences in the assemblage. Polychaete species have been found to a depth of up to 30 cm in the sediment. Nevertheless, most of them (89%) occurred in the upper 5 cm of the sediment, with an increase of specimens in deeper layers in February (i.e. due to sporadic episodes of higher hydrodynamics). To compare the vertical distribution of polychaetes, additional core samples were collected in two seagrass meadows (i.e. C. nodosa and Ruppia cirrhosa) at Ebros Delta (NW Mediterranean); these were separated into five layers (i.e. 0–5 cm, 5–10 cm, 10–15 cm, 15–20 cm, 20–25 cm). The results obtained for the R. cirrhosa meadow (98% of the polychaetes within the upper 5 cm) agree with those for the Canarian C. nodosa meadow, while the polychaetes reached up to 15 cm depth in the Mediterranean C. nodosa meadow (i.e. ~39% between 0 and 5 cm, ~41% between 5 and 10 cm, ~20% between 10 and 15 cm). Our results indicated that the structural characteristics of the assemblages appeared to be more strongly controlled by the combined characteristics of the sediment (i.e. lack of oxygen, granulometry and degree of compaction) than by the seagrass species building the meadow.Communicated by O. Kinne, Oldendorf/Luhe     

Alteration of photosystem II activity by atrazine on Chlamydomonas reinhardtii synchronized and asynchronized cell cycle cultures

Inhibition of photosystem II (PSII) activity by atrazine was investigated in the green alga Chlamydomonas reinhardtii during different states of the cell cycle. The algal cultures were maintained under continuous light or under light/dark cycle (16/8?h) to obtain homogenized cell cycle distribution. The cycle state of algal population was determined by the DNA content using flow cytometry and defined as newly divided cells before the initiation of DNA replication (G₀/G₁) and cells at the end of the replication cycle with fully duplicated DNA content (G₂/M). Under different synchronized states of the cell population, the photosynthetic activity was investigated after treatment at 10, 100, and 1000?µmol?L^?1 atrazine exposed for 24?h by using fluorescence parameters related to PSII activity measured with a plant efficiency analyzer and pulse-amplitude modulated methods. In this study, we found that the atrazine effect was different depending on cell cycle phases and the period of illumination. Algal cells under light–dark cycle showed inhibition of the PSII electron transport leading to an increase of heat energy dissipation by the PSII reaction center. Algal cells grown under continuous light was shown to be more resistant to atrazine than the cells grown under light–dark cycle.     

GC-MS测定土壤中阿特拉津、六氯苯等十种农药残留

建立了气相色谱-质谱-选择离子监测(GC-MS-SIM)同时测定土壤中10种农药(三嗪类除草剂、酰胺类除草剂和有机氯农药)的多残留分析方法.样品采用正己烷/丙酮(1:1,V/V)超声提取、氟罗里硅土柱层析净化、GC-MS-SIM测定.10种农药在0.01(0.02)-1.0(2.0)mg·l~(-1)范围内线性良好,相关系数介于0.9963-0.9998之间;在10,50和250 ng·g~(-1)添加水平下,平均回收率介于81%-117%之间,相对标准偏差均小于14.4%;方法检出限达到ppb至sub-ppb级(0.1-1.3 ng·g~(-1)).将此方法应用于辽宁省不同性质土壤中70个实际土壤样品的分析,阿特拉津、乙草胺、六氯苯、丁草胺、狄氏剂和艾氏剂有检出,该法对不同性质土壤具有广泛适用性.     

Effect of body mass,temperature and food deprivation on oxygen consumption rate of common cuttlefish <Emphasis Type="Italic">Sepia officinalis</Emphasis>

Predictions of short and long term changes in Sepia officinalis metabolism are useful, since this species is both economically important for aquaculture and also is an ideal experimental laboratory organism. In this study standard and routine oxygen consumption rates of newly hatched and juvenile laboratory raised cuttlefish S. officinalis ranging between 0.04 and 18.48 g dry body mass (Dm), were measured over a range of temperatures (10, 15, 20 and 25°C). The mass exponent (b) ranged between 0.706 and 0.992 for standard oxygen consumption and between 0.694 and 0.990 for routine oxygen consumption. Oxygen consumption scaled allometrically (b = 0.7) with body mass for cuttlefish <2 g Dm and isometrically (b = 1) thereafter. No significant differences were apparent amongst the slopes of oxygen consumption and body mass at different temperatures for standard and routine oxygen consumption. However, the intercepts differed significantly amongst the regression lines, indicating a significant effect of temperature on the magnitude of oxygen consumption. The combined effect of temperature (T) and dry body mass (Dm) are best described by the following equations: cuttlefish <2 g, MO₂ = 0.116Dm^0.7111.086 ^T and >2 g, MO₂ = 0.076Dm^0.9831.091 ^T for standard oxygen consumption; cuttlefish <2 g, MO₂ = 0.538Dm^0.7291.057 ^T and >2 g, MO₂ = 0.225Dm^0.9621.081 ^T for routine oxygen consumption. Using these equations it was estimated that a cuttlefish of 1 g Dm held at 20°C, eating 5% Dm day⁻¹ and undergoing standard and routine metabolism consumes 21.3 and 35.4%, respectively of its total daily energy intake. Juvenile cuttlefish (3.32–5.08 g Dm) held at 15°C and deprived of food for 27 days maintained a stable standard oxygen consumption rate for the first 6 days following starvation. By the 18th day without food, oxygen consumption rate had declined by 53% and further declined to 65% below the standard oxygen consumption rate on the 27th day. Upon resumption of feeding, the respiration rate returned immediately to the initial level prior to food deprivation. The present study defines the basic energy requirements and general physiological state of young cuttlefish at temperatures of 10–25°C with and without food.