Photocatalytic treatment of water-soluble pesticides by photo-Fenton and TiO2 using solar energy

The technical feasibility and performance of photocatalytic degradation of four water-soluble pesticides (diuron, imidacloprid, formetanate and methomyl) have been studied at pilot scale in two well-defined systems of special interest because natural-solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. The pilot plant is made up of compound parabolic collectors (CPCs) specially designed for solar photocatalytic applications. Experimental conditions allowed disappearance of pesticide and degree of mineralisation achieved in the two photocatalytic systems to be compared. In order to assure that the photocatalytic results are consistent, hydrolysis and photolysis tests have been performed with the four pesticides. The initial concentration tested with imidacloprid, formetanate and methomyl was 50 and 30 mg/l with diuron, and the catalyst concentrations were 200 mg/l and 0.05 mM with TiO₂ and iron, respectively. Total disappearance of the parent compounds and 90% mineralisation have been attained with all pesticides tested, methomyl being the most difficult to be degraded with both treatments. First-order rate constants, initial rate, time necessary for mineralising 90% of the initial TOC and hydrogen peroxide consumption were calculated in all cases, enabling comparison both of treatments and of the selected pesticide reactivity.     

Concentration of Antifouling Biocides and Metals in Sediment Core Samples in the Northern Part of Hiroshima Bay

Accumulation of Ot alternative antifoulants in sediment is the focus of this research. Much research had been done on surface sediment, but in this report, the accumulation in the sediment core was studied. The Ot alternative antifoulants, Diuron, Sea-Nine211, and Irgarol 1051, and the latter’s degradation product, M1, were investigated in five samples from the northern part of Hiroshima Bay. Ot compounds (tributyltin (TBT) and triphenyltin (TPT)) were also investigated for comparison. In addition, metal (Pb, Cu, Zn, Fe and Mn) levels and chronology were measured to better understand what happens after accumulation on the sea floor. It was discovered that Ot alternative antifoulant accumulation characteristics in sediment were like Ot compounds, with the concentration in the sediment core being much higher than surface sediment. The concentration in sediment seems to have been affected by the regulation of Ot compounds in 1990, due to the concentration of Ot alternative antifoulants and Ot compounds at the survey point in front of the dock, showing an increase from almost the same layer after the regulation.     

Pesticide contamination and phytotoxicity of sediment interstitial water to tropical benthic microalgae

Many organic compounds including some herbicides concentrate in sediment, thus it may be expected that interstitial waters contain higher concentrations of these contaminants than the water column. To estimate benthic microalgal exposure to pesticides, sediment and interstitial water sampled in the dry season from four major rivers in north Queensland, Australia, were analysed for these contaminants. Interstitial water extracts from the sediments were tested for acute phytotoxicity to benthic microalgae using PAM fluorometry and the results were compared with chemical analyses of the same water samples. A range of pesticides were detected in both sediment and interstitial waters from all sites, notably the herbicide diuron at concentrations ranging from 0.3 to 11 μg kg⁻¹ dry weight sediment, and up to 68 ng L⁻¹ in interstitial waters. Herbicide concentrations estimated from partition coefficients and the sediment concentrations typically overestimated analytically determined concentrations present in interstitial water by an order of magnitude. The analytically determined herbicide concentrations in the interstitial water explained most of the phytotoxicity measured with the bioassay; however, photoinhibition was slightly higher than expected based on analytical results, indicating the presence of unidentified phytotoxins. These results demonstrate the presence of pesticides in interstitial waters in the Tropical dry season, sometimes at concentrations that may affect sensitive benthic organisms, and supports the use of the I-PAM bioassay as a valuable tool in exposure- and environmental risk- and impact-assessments.     

Interactions of diuron with dissolved organic matter from organic amendments

Diuron is frequently detected in some drinking water reservoirs under the Burgundy vineyards, where organic amendments are applied. The environmental effect of these amendments on pesticide transport is ambiguous: on the one hand it could enhance their retention by increasing soil organic carbon content; on the other hand, dissolved organic matter (DOM) could facilitate their transport. Elutions were performed using columns packed with glass beads in order to investigate DOM-diuron interactions, and the possible co-transport of diuron and DOM. Four organic amendments (A, B, C and D) were tested; C and D were sampled at fresh (F) and mature (M) stages. An increase in diuron leaching was observed only for A and D_F amendments (up to 16% compared to the DOM-free blank samples), suggesting a DOM effect on diuron transport. These results could be explained by the higher DOM leaching for A and D_F compared to B, C_F, C_M and D_M increasing diuron-DOM interactions. These interactions seem to be related to the aromatic and aliphatic content of the DOM, determining formation of hydrogen and non-covalent bonds. The degree of organic matter maturity does not seem to have any effect with amendment C, while a reduction in diuron leaching is observed between D_F and D_M. After equilibrium dialysis measurement of diuron-DOM complexes, it appeared that less than 3% of the diuron applied corresponded to complexes with a molecular weight > 1000 Da. Complexes < 1000 Da could also take part in this facilitated transport.     

Resistance and recovery of river biofilms receiving short pulses of Triclosan and Diuron

The effects of the herbicide Diuron (DIU) and the bactericide Triclosan (TCS) were assessed on laboratory-grown stream biofilms. Four week-old biofilms were exposed in mesocosms to 48-hours of short pulses of either DIU or TCS. The direct and indirect effects of each toxicant on the biofilms, and the subsequent recovery of the biofilms, were evaluated according to structural and functional biomarkers. These parameters were analyzed immediately before exposure, immediately after exposure, and 9 and 16 days post-exposure. DIU caused an increase in diatom mortality (+ 79%), which persisted until the end of the experiment. TCS also affected diatom mortality (+ 41%), although the effect did not appear until 1 week post-exposure. TCS caused an increase in bacterial mortality (+ 45%); however, this parameter returned to normal values 1 week post-exposure. TCS compromised the cellular integrity of the green alga Spirogyra sp., whereas DIU did not. TCS also strongly inhibited phosphate uptake (− 71%), which did not return to normal values until 2 weeks post-exposure. DIU directly affected algae, but barely affected the heterotrophs, whereas TCS seriously impaired bacteria (direct effect) as well as autotrophs (indirect effect). However, the biofilms recovered their normal structure and function within only a few days to a few weeks. These findings demonstrate the capacity of biofilms to cope with periodic inputs of toxicants, but also the risks associated to repeated exposure or multi-contamination in aquatic ecosystems.     

RESEARCH NOTE: Ozone Degradation Of Selected Non-Agricultural Herbicides

This research note investigates the efficiency of ozone for the degradation of threeherbicides, imazapyr[2-(4-isopropyl-4-methyl-S-oxo-2-imidazolin-2-yl)-nicotinic acid], triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] under controlled laboratory conditions. Experiments were conducted at pH 7.5, in a bubble contactor column, with a raw lowland surface water spiked with initial active ingredient concentrations of 2 μgL^?1. The ozone doses applied and consumed were 4.79 and 2.9 mg O₃L^?1 respectively, and resulted in removals of 53%, 48% and 90% of imazapyr, triclopyr and diuron, respectively.     

Electrokinetic removal of 2,6-dichlorophenol and diuron from kaolinite and humic acid-clay system

This paper presents the results of a study on the electrokinetic treatment of kaolinite and humic acid kaolinite complexes spiked with 2,6-dichlorophenol or 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron). In particular, the attention was paid to the interaction between solid surface and dissolved organics: the effects of contaminant sorption as well as the physicochemical reactions on the efficiency of electrokinetic remediation were investigated. Using a 3V/cm voltage gradient, approximately 90% of diuron was removed from kaolinite after one water pore volume was collected in the cathode reservoir, but much lower efficiency was obtained in the electrokinetic removal of this compound from humic acid-coated kaolinite. The results also showed that partial degradation of the contaminant occurred during electrokinetic treatment of kaolinite clay spiked with 2,6-dichlorophenol: the contamination in the clay could be remediated by the combination of electrokinetic extraction and electrochemical reactions.     

敌草隆和莠去津除草效果及其对海蔗22号苗期生长的影响

以优良品种海蔗22号作为供试材料,在苗期喷施除草剂敌草隆和莠去津,结果表明:敌草隆对于甘蔗栽培过程中常见的单子叶和双子叶杂草均有较好的除杀效果,而莠去津对于甘蔗栽培过程中常见的单子叶杂草除杀效果较差,对双子叶杂草除杀效果尚可。其中,以1.0 g/L敌草隆药液喷施,除草效果较佳。敌草隆和莠去津的喷施对于海蔗22号苗期的株高具有一定的抑制作用,而杂草的减少,有利于海蔗22号苗期干物质的积累。