2,4-D二甲胺盐对莲草直胸跳甲生存和繁殖的影响

为探究除草剂在防治喜旱莲子草(Alternanthera philoxeroides)的过程中对其天敌昆虫的影响,采用不同浓度的2,4-D二甲胺盐浸叶处理的喜旱莲子草饲喂莲草直胸跳甲,连续饲喂7d后,考察了莲草直胸跳甲的繁殖、存活和发育情况。结果表明,2,4-D二甲胺盐可显著降低莲草直胸跳甲成虫的取食量,且抑制作用随药剂浓度升高和取食时间延长而显著增强;较高浓度(1.72～3.44g·L~(-1))的2,4-D二甲胺盐还会导致莲草直胸跳甲雌成虫存活率和产卵量的明显降低,卵孵化率、幼虫存活率和蛹羽化率也显著降低。可见,高浓度(1.72～3.44g·L~(-1))的2,4-D二甲胺盐对莲草直胸跳甲的生长发育和繁殖有显著不利影响,在防治喜旱莲子草时,应将2,4-D二甲胺盐的施用浓度控制在0.22～0.86g·L~(-1)内。     

BSA体系中2,4-D和阿特拉津对性激素的干扰机理

在2,4-D和阿特拉津以及天然性激素(雌二醇、睾酮)中加入牛血清白蛋白(BSA),通过紫外吸收峰的变化、温度与体系荧光强度的关系、以及计算扩散碰撞猝灭常数Kq等方法确定2,4-D和阿特拉津均可以发生类似天然性激素和BSA间的基态络合.并通过双倒数公式计算出各自二元体系的结合常数.2,4-D、阿特拉津、雌二醇、睾酮与BSA的结合常数(K)均在104数量级,可以认为2,4-D和阿特拉津具有与天然性激素相近的对BSA结合能力,并可通过竞争占据结合位点的方式干扰正常性激素与BSA的结合.     

Effect of 2,4-dichlorophenoxyacetic acid on growth, protein and chlorophyll-a content of Chlorella vulgaris and Spirulina platensis cells

In this study, effect of different 2,4 -dichlorophenoxyacetic acid (2,4-D) concentrations (0.0, 9.10(-5), 9.10(-4), 9.10(-3) and 9.10(-2) mM) on growth rate, content of protein and chlorophyll-a in Chlorella vulgaris and Spirulina platensis cells was investigated. The most stimulatory effect on growth rate, protein and pigment ratio of C. vulgaris and S. platensis was observed at 9.10(-4) mM concentrations of 2,4-D. The results show that low concentrations of 2,4-D have hormonal effect due to being a synthetic auxin. Cell number protein and pigment rates were inhibited at 9.10(-2) mM concentration in C. vulgaris. Such parameters were inhibited in S. platensis, both at 9.10(-3) and 9.10(-2) mM 2,4-D concentrations. This is due to herbicidal effect of high concentrations of 2,4-D. S. platensis was found to be more sensitive than S. vulgaris to 2,4-D applications. The use of algae as bio-indicators in herbicide contaminated fresh water habitats, was discussed.     

High amounts of free aromatic amino acids in the protein-like fluorescence of water-dissolved organic matter

Fluorescence spectroscopy is widely used to study water pollution. The fluorescence of water natural organic matter can be classified into two groups: the protein-like fluorescence originating from aromatic amino acids and the humic fluorescence originating from humic substances. Actually, the precise molecular origin of the protein-like fluorescence is unknown because this fluorescence may be caused by either free amino acids, peptides or proteins. Therefore, we studied the molecular origin of the protein-like fluorescence of Suwannee River natural organic matter and fractions A, B and C + D obtained by size exclusion chromatography/polyacrylamide gel electrophoresis. Fractions were analyzed by reversed-phase high-performance liquid chromatography. The electrophoretic mobilities of fractions varied in the order C + D > B > A and the molecular size in the opposite order. Our results show that the protein-like fluorescence is almost exclusively located in high molecular size fraction A and medium molecular size fraction B. Retention times and fluorescence emission spectra of authentic free aromatic amino acids tyrosine and tryptophan were identical with the retention times and emission spectra of several chromatographic peaks of fractions A and B. More than 50 % of the protein-like fluorescence is due to free aromatic amino acids incorporated in water natural organic matter.     

A protein signal triggers sexual reproduction in Brachionus plicatilis (Rotifera)

The defining feature of the life cycle in monogonont rotifers such as Brachionus plicatilis (Muller) is alternation of asexual and sexual reproduction (mixis). Why sex is maintained in such life cycles is an important unsolved evolutionary question and one especially amenable to experimental analysis. Mixis is induced by a chemical signal produced by the rotifers which accumulates to threshold levels at high population densities. The chemical features of this signal were characterized using size exclusion, enzymatic degradation, protease protection assays, selective binding to anion ion exchange and C3 reversed phase HPLC columns, and the sequence of 17 N-terminal amino acids. These studies were carried out over two years beginning in 2003 using B. plicatilis Russian strain. When rotifer-conditioned medium was treated with proteinase K, its mixis-inducing ability was reduced by 70%. Proteinase K was added to medium auto-conditioned by 1 female ml⁻¹ where typically 17% of daughters became mictic and mixis was reduced to 1%. A cocktail of protease inhibitors added to conditioned medium significantly reduced degradation of the mixis signal by natural proteases. Conditioned medium subjected to ultrafiltration retained mixis-inducing activity in the >10 kDa fraction, but the <10 kDa fraction had no significant activity. The putative mixis signal bound to an anion exchange column, eluting off at 0.72 M NaCl. These fractions were further separated on a C3 reversed phase HPLC column and mixis-inducing activity was associated with a 39 kDa protein. Seventeen amino acids from the N-terminus have strong similarity to a steroidogenesis-inducing protein isolated from human ovarian follicular fluid. The 39 kDa protein is an excellent candidate for the rotifer mixis induction signal.     

间接竞争ELISA方法测定水中2，4-D的研究

以2,4-D-BSA为包被抗原,采用自行制备的2,4-D单克隆特异性抗体6D11建立了水中2,4-D的间接竞争 ELISA检测方法．本研究比较了包被抗原2,4-D-BSA浓度分别为240ng·mL-1、120ng·mL-1和60ng·mL-1的反应体系和竞争反应时间为60min和15min的间接竞争ELISA剂量-反应曲线,确定了当包被抗原浓度为60 ng·mL-1、竞争反应时间为15min时,剂量-反应曲线的IC50值较低．采用上述实验条件分别测定了由PBS缓冲溶液、饮用水、清华大学地下水和圆明园福海地表水配制的2,4-D标准溶液的剂量．反应曲线,发现实际水样的基质效应对检测结果的影响较大;采用实际水样和PBS缓冲溶液配水在含有5％乙醇的PBS缓冲体系中反应的方法,基本上消除了基质效应对检测结果的干扰．采用上述优化试验条件,测定2,4-D浓度分别为0．5mg·L-1、0．125mg·L-1和0．03mg·L-1的加标样品,测定数据的准确度符合痕量有机污染物定量检测对准确度的要求,但是平行样品测定数据之间的变异系数较大,需要进一步改进检测方法,用于实际水样的检测．     

Biofilm-electrode process with high efficiency for degradation of 2,4-dichlorophenol

2,4-Dichlorophenol (2,4-DCP) from chemical industry wastewaters has caused serious environmental pollution. Removal of 2,4-DCP using either physico-chemical or biological methods is not very efficient. In this paper, a combination of biological and electrochemical methods gave satisfactory results. By comparisons of the degradation of 2,4-DCP and the removal of chemical oxygen demand (COD) in electrochemical, biological and biofilm-electrode processes, it was found that the biofilm-electrode process possesses the highest degradation efficiency and removal rate; both the pure electrochemical and the pure biological processes were far less efficient. The removal efficiency of 2,4-DCP using the biofilm-electrode process was 100% in 48 h, while that using the pure electrochemical and the pure biological processes were 62 and 42%, respectively. The experiments show that the current of 5 mA for the cathode of 9 cm² and the initial concentration 100 mg/l of 2,4-DCP were the optimal parameters of technology for the biofilm-electrode process. The excellent effects are due to the withdrawing electron action of bacterium, electrochemically anodic oxidation and cathodic dechlorination. It is the first time that the biofilm-electrode method was applied in 2,4-DCP degradation. Here, we demonstrated that biofilm-electrode process is a promising method to remove some aromatic compounds in industrial wastewater.     

Determination of total and bioaccessible metals in airborne particulate matter from an urban and a rural area at Sarajevo

Airborne particulate matter of up to 10 µm collected at an urban and a rural area at Sarajevo in 2013 and 2014 was acid digested for determination of total concentrations or extracted with synthetic gastric juice for the bioaccessible fractions of Cd, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn and determined by graphite furnace and flame atomic absorption spectrometry. The total concentrations of Cr, Cu, Fe, Mn, Pb, and V were higher at the urban site, while those of Cd, Ni, and Zn were virtually equal at both sites. The average bioaccessible fractions exhibited the following trend at both sites: Fe > Zn > Cu > Mn > Pb > Cr > V > Ni > Cd. Enrichment factors and daily intake of metals by inhalation were calculated.     

Additive und synergistische Kombinationswirkungen von Xenobiotika in subtoxischen Konzentrationen auf menschliche Fibroblasten

The toxic combination effects of xenobiotics of different substance classes were investigated in human fibroblasts. Subtoxic concentrations of 4-chloroaniline enhanced the toxicity of 2,4-dichlorophenoxyacetic acid (2,4-D, dimethylammonium salt) in an additive manner. A mixture of 4-chloroaniline, dicofol and 4-chlorophenol increased the toxicity of 2,4-D synergistically. The concentrations of the components used in the mixture were one third of their ?no observed effect concentrations” (NOEC). The combination of 4-chloroaniline, dicofol and 4-chlorophenol (without 2,4-D) at subtoxic concentrations also showed synergistic effects. The great differences in the lipophilicity of the combined substances might be the cause of the synergistic action.     

A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4-Dichlorophenoxyacetic acid degradation

• A new pulsed switching peroxi-coagulation (PSPC) system was developed. • The EC_T for 2,4-D removal in the PSPC was lower than that in the EF. • The iron consumption for 2,4-D removal in the PSPC was lower than that in the PC. The aim of this study was to develop a new pulsed switching peroxi-coagulation system to control hydroxyl radical (?OH) production and to enhance 2,4-Dichlorophenoxyacetic acid (2,4-D) degradation. The system was constructed with a sacrifice iron anode, a Pt anode, and a gas diffusion cathode. Production of H₂O₂ and Fe²⁺ was controlled separately by time delayers with different pulsed switching frequencies. Under current densities of 5.0 mA/cm² (H₂O₂) and 0.5 mA/cm² (Fe²⁺), the ?OH production was optimized with the pulsed switching frequency of 1.0 s (H₂O₂):0.3 s (Fe²⁺) and the ratio of H₂O₂ to Fe²⁺ molar concentrations of 6.6. Under the optimal condition, 2,4-D with an initial concentration of 500 mg/L was completely removed in the system within 240 min. The energy consumption for the 2,4-D removal in the system was much lower than that in the electro-Fenton process (68±6 vs. 136±10 kWh/kg TOC). The iron consumption in the system was ~20 times as low as that in the peroxi-coagulation process (196±20 vs. 3940±400 mg/L) within 240 min. The system should be a promising peroxi-coagulation method for organic pollutants removal in wastewater.     

Degradation of bisphenol A by photo-fenton processes

The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H₂O₂ by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H₂O₂ only, 32% of BPA was degraded after 120?min of irradiation. However, 97% of BPA was degraded in the presence of both H₂O₂ and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H₂O₂. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.     

除草剂对优质小麦品质和旗叶保护酶的调控效应

通过田间试验研究了4种除草剂在正常剂量下对2个优质小麦品种品质性状、蛋白质组分和旗叶保护酶系的影响.结果表明,整个籽粒灌浆过程中,2,4-D丁酯处理使籽粒蛋白质含量一直较高,世玛处理在灌浆前中期籽粒蛋白质含量较高,但灌浆末期籽粒蛋白质含量最低,巨星和骠马处理影响较小.2,4-D丁酯处理使收获时籽粒蛋白质含量及组分最高,湿面筋含量、沉降值、吸水率、稳定时间和评价值等加工品质最好,世玛处理则使营养品质和加工品质最差,巨星和骠马处理影响相对较小.籽粒灌浆期间,2,4-D丁酯处理使旗叶SOD、CAT和POD活性一直较低,尤其是籽粒灌浆末期活性最低;其它除草剂使旗叶SOD、CAT和POD活性在不同灌浆时期存在差异:灌浆前中期,骠马处理使3种保护酶活性最高;灌浆后期,世玛处理使旗叶中保护酶活性下降缓慢,且活性最高.籽粒灌浆期前期,4种除草剂对旗叶中MDA含量的影响是:世玛＞骠马＞CK＞巨星＞2,4-D丁酯,灌浆中后期,2,4-D丁酯和巨星处理使MDA含量快速提高,世玛和骠马处理使MDA含量升高相对较慢,到灌浆末期,2,4-D丁酯使MDA含量最高,世玛处理最低.图5表2参22     

Speciation study of trace elements in surface sediment of Winam Gulf,Lake Victoria,by sequential extraction,aqua-regia acid digestion,and ICP-OES

The speciation of trace metals in surface sediment in Kisumu Carwash area of Winam Gulf, was studied and results compared with those found at Usoma beach which was found to be several orders of magnitude less polluted. High proportions of the metals were bioavailable (fractions 1–6) with BA% ranging from 21.7% (Al) to 94.5% (Pb) at Carwash and 19.6% (Al) to ～100% (for Cd and Pb) at Usoma beach. The readily mobilizable fraction (fractions 1–4) decreased in the order: Pb > Mn > Sn > Cu > Co > Zn > Mg > Cd > Mo > Ni > Cr > Fe > Al at Carwash and Mn > Mo > Sn > Pb > Cd > Mg > Cu > Zn > Co > Ni > Fe > Cr > Al at Usoma beach. The total Zn, Cd, Cr, and Cu sediment concentrations at Carwash were higher than the threshold effect concentrations (TECs), although their bioavailable concentrations were lower than these limits. Both the total and bioavailable concentrations of Pb in surface sediment at Kisumu Carwash area were higher than the TEC threshold limit indicating significant contamination from this heavy metal. Although there was a general good agreement on data obtained by sequential extraction as compared with those obtained by direct aqua-regia digestion, there were large discrepancies for some specific metal analytes which could be accounted for in terms of analytical variations and lack of uniformity in physical and chemical composition of the sediment samples analyzed.     

Degradation of dye rhodamine B under visible irradiation with Prussian blue as a photo-Fenton reagent

Rhodamine B can be degraded using Prussian blue as a photo-Fenton like reagent under λ > 420 nm visible irradiation. Kinetic studies show ln(C _o/C _t ) is linearly proportional to the reaction time during the photo-degradation process; thus, the degradation reaction obeys a pseudo-first order kinetic law. It is very interesting that the presence of salinity such as 0.1 M KCl can speed up greatly the degradation rate: the time to achieve 90.0% degradation ratio is shortened from 120.0 to 40.0 min under comparable conditions, which is very useful in the treatment of wastewaters with high content of salinity.     

Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.     

Remediation of 2,4-dichlorophenol-contaminated groundwater using nano-sized CaO2 in a two-dimensional scale tank

• Nano CaO₂ is evaluated as a remediation agent for 2,4-DCP contaminated groundwater. • 2,4-DCP degradation mechanism by different Fe²⁺ concentration was proposed. • 2,4-DCP was not degraded in the system for solution pH>10. • The 2,4-DCP degradation area is inconsistent with the nano CaO₂ distribution area. This study evaluates the applicability of nano-sized calcium peroxide (CaO₂) as a source of H₂O₂ to remediate 2,4-dichlorophenol (2,4-DCP) contaminated groundwater via the advanced oxidation process (AOP). First, the effect and mechanism of 2,4-DCP degradation by CaO₂ at different Fe concentrations were studied (Fenton reaction). We found that at high Fe concentrations, 2,4-DCP almost completely degrades via primarily the oxidation of •OH within 5 h. At low Fe concentrations, the degradation rate of 2,4-DCP decreased rapidly. The main mechanism was the combined action of •OH and O₂^•−. Without Fe, the 2,4-DCP degradation reached 13.6% in 213 h, primarily via the heterogeneous reaction on the surface of CaO₂. Besides, 2,4-DCP degradation was significantly affected by solution pH. When the solution pH was>10, the degradation was almost completely inhibited. Thus, we adopted a two-dimensional water tank experiment to study the remediation efficiency CaO₂ on the water sample. We noticed that the degradation took place mainly in regions of pH<10 (i.e., CaO₂ distribution area), both upstream and downstream of the tank. After 28 days of treatment, the average 2,4-DCP degradation level was ≈36.5%. Given the inadequacy of the results, we recommend that groundwater remediation using nano CaO₂: (1) a buffer solution should be added to retard the rapid increase in pH, and (2) the nano CaO₂ should be injected copiously in batches to reduce CaO₂ deposition.     

An investigation into the occurrence and distribution of polycyclic aromatic hydrocarbons in two soil size fractions at a former industrial site in NE England,UK using in situ PFE–GC–MS

Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in 16 topsoils (0–10 cm) collected across the site of a former tar works in NE England. The soils were prepared in the laboratory to two different particle size fractions: <250 μm (fraction A) and >250 μm to <2 mm (fraction B). Sixteen priority PAHs were analysed in the soils using in situ pressurised fluid extraction (PFE) followed by gas chromatography—mass spectrometry (GC–MS). The average total PAH concentration in the soils ranged from 9.0 to 1,404 mg/kg (soil fraction A) and from 6.6 to 872 mg/kg (soil fraction B). These concentrations are high compared with other industrially contaminated soils reported in the international literature, indicating that the tar works warrants further investigation/remediation. A predominance of higher-molecular-weight compounds was determined in the samples, suggesting that the PAHs were of pyrogenic (anthropogenic) origin. Statistical comparison (t-test) of the mean total PAH concentrations in soil fractions A and B indicated that there was a significant difference (95% confidence interval) between the fractions in all but two of the soil samples. Additionally, comparisons of the distributions of individual PAHs (i.e. 16 PAHs × 16 soil samples) in soil fractions A and B demonstrated generally higher PAH concentrations in fraction A (i.e. 65.8% of all individual PAH concentrations were higher in soil fraction A). This is important because fraction A corresponds to the particle size thought to be most important in terms of human contact with soils and potential threats to human health.     

Evidences showing 2,4-D ethyl ester and pencycuron-induced DNA damage in cyanobacteria and detection by PCR

The impact of 2,4-D ethyl ester and pencycuron in inducing DNA damage in three species of cyanobacteria-Anabaena fertilissima, Aulosira fertilissima, and Westiellopsis prolifica as evidenced by PCR-based assays: RAPD and 16S rRNA amplification was examined. Exposure of genomic DNA (in vitro) to pencycuron for 4 days did not produce severe damage in DNA fragments of all three cyanobacterial species whereas exposure to 2,4-D ethyl ester markedly inhibited the template activity of genomic DNA compared to untreated cultures of A. fertilissima. In A. fertilissima a single band of approximately 1000?bp was observed even after 16 days of exposure to 60?ppm pencycuron which suggests that certain segments of DNA are resistant to pencycuron DNA damaging effects. However, a significant effect was observed in the case of W. prolifica for 2,4-D ethyl ester and pencycuron where complete disappearance of fragments was not recorded even after 16 days of incubation and interestingly some new DNA bands were induced. Similar to the effects with RAPD profile, amplification of rRNA was significantly inhibited following exposure of genomic DNA to 2,4-D ethyl ester and pencycuron. Our findings clearly demonstrate that pesticide concentrations affected cyanobacterial DNA and lethality of these microbes might be due to irreversible DNA damage. Thus, it is postulated that PCR assays may be conveniently used for screening DNA damage produced by 2,4-D ethyl ester and pencycuron in all three cyanobacteria examined in this study.     

竹炭对2,4-二氯苯酚的吸附特性及影响因素研究

研究了水溶液中竹炭对 2 ,4-二氯苯酚的吸附特性及其影响因素。结果表明 ,竹炭对 2 ,4-二氯苯酚具有较强的吸附性能 ,吸附效果与竹炭粒径、用量、污染物浓度以及吸附平衡时间和平衡方式有关。     

Chemical defence in chewing and sucking insect herbivores: Plant-derived cardenolides in the monarch butterfly and oleander aphid

Summary Cardenolide sequestration by a hemimetabolous aphid and a holometabolous butterfly from the neotropical milkweed,Asclepias curassavica L., is compared. The oleander aphid,Aphis nerii B. de F., sequestered a similarly narrow range of cardenolide concentrations to the monarch butterfly,Danaus plexippus (L.), from the wide range of concentrations available in leaves of A.curassavica. However, A.nerii sequestered significantly less cardenolide (269 µg/0.1 g) thanD. plexippus (528 µg/0.1 g). The honeydew excreted by A.nerii was comprised of 46% cardenolide. The complete polarity range of 25 cardenolides detected by thin layer chromatography in A.curassavica was represented in the 17 whole aphid cardenolides and the 20 aphid honeydew cardenolides detected. D.plexippus sequestered a narrower polarity range of 11 cardenolides, having eliminated low polarity cardenolide genins and glycosides. It is suggested that these chemical differences may be related to interactions among the broad feeding tactics of sucking or chewing milkweed leaves, life history constraints of holometabolyversus hemimetaboly, the distribution of milkweed food resources in space and time, and the dynamics of natural enemies.