Simultaneous voltammetric determination of four triazine herbicides in water samples with the aid of chemometrics

A novel differential pulse voltammetry (DPV) method was developed for the simultaneous analysis of herbicides in water. A mixture of four herbicides, atrazine, simazine, propazine and terbuthylazine was analyzed simultaneously and the complex, overlapping DPV voltammograms were resolved by several chemometrics methods such as partial least squares (PLS), principal component regression (PCR) and principal component–artificial networks (PC–ANN). The complex profiles of the voltammograms collected from a synthetic set of samples were best resolved with the use of the PC–ANN method, and the best predictions of the concentrations of the analytes were obtained with the PC-ANN model (%RPE_T = 6.1 and average %Recovery = 99.0). The new method was also used for analysis of real samples, and the obtained results were compared well with those from the GC-MS technique. Such conclusions suggest that the novel method is a viable alternative to the other commonly used methods such as GC, HPLC and GC-MS.     

THE EFFECTS OF DIPOTASSIUM ENDOTHALL ON THE ZOOPLANKTON AND WATER QUALITY OF A SMALL POND1

ABSTRACT: Zooplankton samples and dissolved oxygen-temperature readings and water samples were taken from a treatment and control pond on 41 and 42 separate occasions, respectively, both before and after the application of 5.0 mg/l (a.i.) dipotassium endothall to the 0.31 ha treatment pond on May 31, 1973. Seasonal fluctuations in the density of Cladocera and Copepoda coincided quite closely in both ponds and were similar to the fluctuations reported in the literature to be typical of temperate region ponds and lakes. An apparent seasonal shift in generic composition from .Daphnia spp. in May to Ceriodaphnia spp. in June to Chydorus spp. from July/early September occurred in both ponds and is thought to be at least partially due to fish predation. No apparent changes in species composition or generic densities of Cladocerans was noted in the treatment pond that did not also occur in the control pond. There were no noticeable effects of the dipotassium endothall on either the Calanoida or Cyclopoida suborders of Copepoda. A later pulse of Ostracoda in the treatment pond, when compared to the control, may have been due to the dipotassium endothall or to a combination of the effects of the herbicide on the macrophytes and the method of sampling. A decrease in dissolved oxygen below saturation, occurring in the treated pond from 3–21 days after treatment, was attributed to an increase in biological oxygen demand associated with weed-kill. There was no noticeable increase in plant nutrients (N and P) in the treated pond following herbicide application, nor were there any apparent changes in the other chemical parameters studied.     

FACTORS AFFECTING HERBICIDE YIELDS IN THE CHESAPEAKE BAY WATERSHED,JUNE 19941

ABSTRACT: Median concentrations and instantaneous yields of alachlor, metolachlor, atrazine, cyanazine, and simazine were generally highest at sites in the Lower Susquehanna River Basin and in agricultural subbasins. Instantaneous herbicide yields are related to land use, hydrogeologic setting, streamflow yield, and agricultural row cropping practices. The significance of these relations may be affected by the interdependence of the factors. The percentage of basin area planted in corn is the most influential factor in the prediction of herbicide yield. Instantaneous yields of all five herbicides measured in June 1994 related poorly to averaged 1990–94 herbicide use. Annually averaged herbicide-use data are too general to use as a predictor for short-term herbicide yields. An evaluation of factors affecting herbicide yields could be refined with more-current land use and land cover information and a more accurate estimate of the percentage of basin area planted in corn. Factors related to herbicide yields can be used to predict herbicide yields in other basins within the Chesapeake Bay watershed and to develop an estimate of herbicide loads to Chesapeake Bay.     

EFFECTS OF FOREST HERBICIDE APPLICATIONS ON STREAMWATER CHEMISTRY IN SOUTHWESTERN BRITISH COLUMBIA1

ABSTRACT: The herbicide glyphosate was applied to portions of two watersheds in southwestern British Columbia to kill vegetation that was competing with Pseudotsuga menziesii (Douglas-fir) plantations. This application had little significant effect on streamwater chemistry (K⁺, Na²⁺, Mg²⁺, Ca²⁺, Cl^-, NOs₃^-, NH₄⁺, PO4^3-, SO₄⁼, and SiO₂ concentrations, electrical conductivity, and pH) when vegetation cover in a watershed was reduced by 4%, but had significant (P>0.05) effects, which lasted for at least five years, when cover was reduced by 43%. In this case, most parameters increased in value following the application, with K⁺ and Mg²⁺ concentrations and pH values exhibiting the most prolonged increases and NO₃^- concentrations exhibiting the greatest percentage increases. Sulphate and dissolved SiO₂ concentrations decreased following the application. Streamwater chemical fluxes showed similar trends to concentrations except that changes in fluxes were less significant and no decreases were observed. Forest management induced losses of NO₃-N in streamwater during the first five post-treatment years in the study area decreased in the order: herbicide application (approximately 40 kg/ha) < clearcutting and slashburning (approximately 20 kg/ha) < clearcutting (approximately 10 kg/ha). In watersheds similar to those of the study area, herbicide application is likely to have a greater impact on streamwater chemistry, in general, than would clearcutting or clearcutting followed by slashburning.     

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Abstract

The leaching behaviour of the herbicide acetochlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(ethoxymethyl)acetamide] was determined as compared with two congener compounds, alachlor [2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxymethyl)acetamide] and metolachlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide]. The leaching profiles of the herbicides in columns with different types of soil and their capacity factors in reverse phase HPLC were compared. An approach for preliminary characteristic of the potential for water pollution of acetochlor is presented. The herbicide is classified as a leacher in soil and its potential for contamination of ground water is comparable with those of alachlor and metolachlor.     

Air concentrations of currently used herbicides and legacy compounds in the Canadian prairies,subarctic, and arctic

Passive air samplers were installed in the summers of 2005 and 2007 for 90 days at four locations in the agricultural region of the Canadian Prairies and at five locations in the Canadian Subarctic and Arctic. The presence and masses of ten currently used herbicides and three legacy compounds in the polyurethane foam disks were quantified. Herbicides 2,4-D, bromoxynil and MCPA were detected at all locations in the Canadian Prairies and in both years because these herbicides are widely applied to control broadleaf weeds in cereal crops that are an integral part of Prairie agricultural production systems. MCPA was also detected at one location in the Arctic in 2007. The detection of the other seven herbicides in the 2 years combined ranged from no detections (atrazine only) to five detections for the relatively volatile herbicides trifluralin and triallate. Triallate was the only other herbicide detected in the Arctic (2005). Legacy compounds were either not detected (alachlor) or at levels near their detection level (γ-HCH and α-HCH). γ-HCH and α-HCH were more frequently detected in 2005 than in 2007 indicating that their concentrations in Canadian air have decreased over time. γ-HCH, widely used as an insecticide in Prairie oilseed production until 2002, was detected at larger concentrations in the Canadian Prairies than in the Subarctic and Arctic. α-HCH, a manufacturing by-product in technical HCH prior to 1971 in Canada, was not detected in the Canadian Prairies but was at detectable levels in the Subarctic and Arctic as the Arctic Ocean is reported to be a major source of α-HCH to the atmosphere. We conclude that some of the most widely used herbicides in Canadian agriculture today are commonly present in the air in regions where they are applied and that a portion of these herbicides may be traveling as parent molecules to the Canadian Arctic. To the authors’ knowledge, this is the first evidence of the presence of MCPA and triallate in Arctic air samples, perhaps because previous research has seldomly monitored for currently used herbicides in this region.     

Triazine and Metolachlor Herbicide Residues in Farm Areas of the Lower Fraser Valley,British Columbia,Canada

Crop soils, ditch sediments and water flowing from several Lower Fraser River (LFR) farm areas of British Columbia, Canada, to salmon tributary streams of that river were sampled in 2004–2005 to quantify for residues of triazine [atrazine, desethylatrazine (a transformation product of atrazine), propazine, and simazine] and metolachlor (a chloroacetamide) herbicides. Average concentrations [μg kg^?1 dry weight (d.w.)] of triazine (10,110) and metolachlor (8,910) herbicides detected in crop soils at the start (May 2004, 2005) of the growing season were about 17 and 6 times, respectively, higher than those found for both herbicide groups during (June–Sept, 2004, 2005) the growing season. In contrast, mean concentrations (μg L^?1) of triazines (0.092) and metolachlor (0.014) in permanent ditches adjacent to farms were about 7 and 28 times, respectively, lower at the start than during the growing season. Both herbicide groups in ditch sediments were detected only during the growing season at concentrations averaging about 315 μg kg^?1 d.w. The risk potential of these herbicides for non-target aquatic organisms inhabiting permanent farm ditches contiguous to tributary streams of the LFR during the growing season is evaluated and discussed.     

Effects of Clear-Cutting and Plant Competition Control Methods on Carabid (Coleoptera: Carabidae) Assemblages in Northwestern Ontario

Total captures, species richness, diversity, and assemblages of adult carabids (Coleoptera: Carabidae) in a boreal mixed-wood ecosystem study were compared among unharvested, and clear-cut plots untreated or treated with herbicides (Vision® and Release®), mechanical treatments (brush saw and Silvana Selective). Carabids were sampled using unbaited pitfall traps for one growing season 7 and 9 years after clear-cutting, in the second growing season after competition control was applied. A total of 5032 individuals representing 30 species were collected between June 1 and September 25, 1995. Total catches were not affected by the harvest or the conifer release alternatives applied. Species richness and diversity increased following conifer release alternatives. Ten species showed habitat preferences after treatment whereas the remaining 20 species were not significantly affected by treatment.     

固相萃取-高效液相色谱法测定水中磺酰脲类除草剂

建立了固相萃取-高效液相色谱测定水中7种磺酰脲类除草剂的方法,考察了降解作用及滤膜对测定的影响.方法在0.30 mg/L～5.00 mg/L之间线性关系良好,7种磺酰脲类除草剂的检出限为0.32 μg/L～0.62 μg/L,RSD为4.4%～7.6%,平均加标回收率为87.9%～102%.     

Effects of herbicides on Odonata communities in a rice agroecosystem

The effects of the five herbicides propanil, quinclorac, molinate/propanil, 2,4-D amine, and bensulfuron on Odonata diversity and abundance at the experimental rice plots was investigated. A total of 13 Odonata morphospecies belonging to two families have been identified. Treated plots exhibited higher species richness (up to 12 species) than the control plot (8 species). Ishnura spp. was the most abundant species in the treated plots with a mean density of 194.2 individuals per m², (ind m^?2) followed by Brachythemis contaminata (152 ind m^?2) and Agriocnemis spp. (124 ind m^?2). In the control plots, Agrocnemis spp. was the dominant species (153 ind m^?2) followed by Ishnura spp. (143 ind m^?2) and Neurothemis fluctuans (59 ind m^?2). In the propanil-treated plot, the highest number of odonate species (10 species) was recorded followed by the plots treated with quinclorax and molinate/propanil (9 species). On the 2,4-D amine or bensulfuron-treated plots as well as the control plot, only eight odonate species were recorded. This study revealed that herbicide application had a positive effect on Odonata diversity. This seems reasonable as Odonata are non-target organisms for herbicides. Furthermore, the decomposed weeds resulting from herbicide application would enrich the water with necessary organic matter.