Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

Effects of glyphosate and foliar amendments on activity of microorganisms in the soybean rhizosphere

A field study was conducted to determine the effects of glyphosate on microbial activity in the rhizosphere of glyphosate-resistant (GR) soybean and to evaluate interactions with foliar amendments. Glyphosate at 0.84 kg ae ha^{? 1} was applied GR soybean at the V4–V5 development stages. Check treatments included a conventional herbicide tank mix (2003 study only) and no herbicides (hand-weeded). Ten days after herbicide application, a commercially available biostimulant and a urea solution (21.0% N) were applied to soybean foliage at 33.5 mL ha^{? 1} and 9.2 kg ha^{? 1}, respectively. Soil and plant samples were taken 0, 5, 10, 15, 20 and 25 days after herbicide application then assayed for enzyme and respiration activities. Soil respiration and enzyme activity increased with glyphosate and foliar amendment applications during the 2002 growing season; however, similar increases were not observed in 2003. Contrasting cumulative rainfall between 2002 and 2003 likely accounted for differences in soil microbial activities. Increases in soil microbial activity in 2002 suggest that adequate soil water and glyphosate application acted together to increase microbial activity. Our study suggests that general soil microbial properties including those involving C and N transformations are not sensitive enough to detect effects of glyphosate on rhizosphere microbial activity. Measurements of soil-plant-microbe relationships including specific microbial groups (i.e., root-associated Fusarium spp.) are likely better indicators of impacts of glyphosate on soil microbial ecology.     

Dissipation of four forest-use herbicides at high latitudes

Background, aim, and scope  Large-scale deforestation is occurring in subarctic North America following clearing by salvage logging or insect attack. Numerous shrubs, herbs, and deciduous tree species tend to dominate areas on which stands of white spruce have grown. In the absence of economically advantageous mechanical methods, several herbicides have value in efforts to reforest by planting white spruce. Glyphosate, imazapyr, triclopyr, and hexazinone are all capable of selectively removing many competing species, but there is concern about whether they would degrade naturally or persist owing to the frigid climate. Materials and methods  We established test plots with all four herbicides in upland and river bottom sites at 65°N and 58°N latitudes. The northern site has extremely cold winters, with soils that freeze to a depth of 1–2 m, and precipitation of 275 mm/year. The southern site has heavy rain and snowfall, amounting to 2,250 mm/year evenly distributed. Soil seldom freezes deeply. On each test plot, one of the four herbicides was applied at twice the normal operational use rate to facilitate detection. They were applied at the normal timing, with hexazinone, imazapyr, and triclopyr applied in June and glyphosate applied in fall. Soils were sampled immediately after treatment and those samples used as references for dissipation data gathered over the next 11–14 months from soil 0- to 15- and 15- to 45-cm depths. Results  Dissipation rates did not follow first-order rates because freezing conditions slowed most microbial activity. All products dissipated to close to or below detection limits within the time of the study. Dissipation from vegetation was substantially more rapid and depended on the nature of the plants treated as well as the product used. While soil residues dissipated more slowly than in temperate regions, they did display consistent dissipation patterns during above-freezing conditions and also the influence of microbial activity. Mobility was very limited with all products but hexazinone. Discussion  These products dissipate during summer in high latitudes much as they would in temperate climates. Winter changes are small, but are not unlike some changes reported elsewhere under freezing conditions. Unlike many other studies, soil water did not influence dissipation heavily, but the high latitude and semi-arid climate also did not create severely droughty soils. Residues in plants were much higher than those in soils, but denatured the vegetation quickly, leading to unsuitability for forage in any case. Conclusions  Low toxicity of these products and their metabolites combined with consistent dissipation and low mobility suggest that toxic hazard of their use at high latitudes need not be a matter of serious concern to humans, terrestrial wildlife, or aquatic systems. They are safe for use in management and rehabilitation of boreal forests when used properly. Recommendations and perspectives  Dissipation at rates approaching those in warmer climates offer a hypothesis that microflora native to high latitudes may be adapted to destruction of such molecules at lower temperatures than may be indicated by experiments with microflora adapted to warmer climates. Residues pose no observable risk to wildlife or humans in the area of use when products are applied properly. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available for authorized users.     

高效液相色谱法测定土壤中三嗪类除草剂

建立了索氏提取、中性氧化铝小柱净化、高效液相色谱二极管阵列检测器测定土壤中7种三嗪类除草剂的方法，优化了检测波长、提取方法和溶剂、梯度淋洗程序等试验条件。7种三嗪类除草剂在0．10mg／L～2．00mg／L范围内线性良好，检出限为0．84μg／kg～2．07μg／kg，RSD为1．2％～5．6％，加标回收率为95.0％～107％。     

Microbial degradation of the benzonitrile herbicides dichlobenil, bromoxynil and ioxynil in soil and subsurface environments--insights into degradation pathways, persistent metabolites and involved degrader organisms

The benzonitriles dichlobenil, bromoxynil and ioxynil are important broad-spectrum or selective herbicides used in agriculture, orchards and public areas worldwide. The dichlobenil metabolite 2,6-dichlorobenzamide is the most frequently encountered groundwater contaminant in Denmark, which suggests that the environmental fate of these three structurally related benzonitrile herbicides should be addressed in detail. This review summarises the current knowledge on microbial degradation of dichlobenil, bromoxynil and ioxynil with particular focus on common features of degradation rates and pathways, accumulation of persistent metabolites and diversity of the involved degrader organisms.     

Postemergence Control of Microstegium vimineum on Riparian Restoration Sites with Aquatic‐Use Registered Herbicides

Microstegium vimineum is an invasive grass introduced from Asia that has spread throughout riparian areas of the eastern United States threatening native riparian vegetation. Postemergence (POST) herbicides registered for aquatic use were evaluated for control of M. vimineum on two riparian restoration sites in the Piedmont and Upper Coastal Plain of North Carolina. This study found that standard and lower than standard rates of diquat, fluridone, flumioxazin, glyphosate, imazamox, and imazapyr reduced weed stem density and biomass at 6 and 30 weeks after treatment (WAT). Both rates of bispyribac and penoxsulam provided less control of M. vimineum. Visual ratings showed both rates of diquat, flumioxazin, imazamox, and imazapyr controlled 63‐100% of M. vimineum at 6 WAT and 84‐100% at 30 WAT. Fluridone and glyphosate provided slightly less control. Bispyribac and penoxsulam treatments provided less control at 6 and 30 WAT compared to the other treatments. Plots treated with both rates of diquat, flumioxazin, imazamox, and imazapyr were nearly devoid of all vegetation at 30 WAT. Recommendations include POST application of lower than standard rates of diquat, flumioxazin, fluridone, glyphosate, imazamox, and imazapyr on riparian restoration sites infested with M. vimineum. Immediate vegetation management measures including temporary and permanent plant cover should be employed on treated sites where weeds are completely eradicated to prevent erosion.     

色谱质谱联用技术在一起农药污染事故应急监测中的应用

在一起污染源应急事故中,色谱质谱联用技术在确定污染源类型,并快速做出准确定性定量分析中发挥了重要作用。通过气相色谱-质谱联用技术,首先确定可能污染物类型为三嗪类化合物;之后,通过液相色谱-串连质谱全扫描,推断可能为三嗪类除草剂——甲磺隆。正、负ESI子离子全扫描后图谱与甲磺隆标准物质图谱相对照,完全吻合。最后,通过SRM模式下对380.0→139.0的母、子离子选择反应监测,测定了农田灌溉水源和土壤中甲磺隆的含量。     

高效液相色谱法测定水中7种三嗪类除草剂

采用液液萃取和固相萃取两种方法预处理,高效液相色谱二极管阵列检测器测定水中7种三嗪类除草剂,选择了合适的检测波长和梯度淋洗条件。方法在0.100 mg/L~2.00 mg/L范围内线性良好,检出限为0.06μg/L~0.15μg/L,水样平行测定的RSD为1.6%~6.5%,加标回收率为95.0%~106%。     

Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process

Abstract

Leaching studies of mecorprop (R,S)‐2‐(4‐chloro‐2‐methylphenoxy)propanoic acid, and dichlorprop, (R,S)‐2‐(4‐chloro‐2,4‐dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods     

Metabolites of the phenylurea herbicides chlorotoluron, diuron, isoproturon and linuron produced by the soil fungus Mortierella sp.

Phenylurea herbicides are used worldwide, and often pollute surface- and groundwater in concentrations exceeding the limit value for drinking water (0.1 μg l⁻¹). Bacteria degrade phenylurea herbicides by successive N-dealkylation to substituted aniline products. Little is known about the corresponding fungal pathways, however. We here report degradation of chlorotoluron, diuron, isoproturon and linuron by the soil fungus Mortierella sp. Gr4. Degradation was fastest with linuron and resulted in successively dealkylated metabolites and 3,4-dichloroaniline. A major new metabolite was detected that has not yet been fully identified. Thin layer chromatography and nuclear magnetic resonance spectroscopy indicate that it is a non-aromatic diol. Degradation of isoproturon, chlorotoluron and diuron involved successive N-demethylation and, in the case of isoproturon and chlorotoluron, additional hydroxylation. A new hydroxylated isoproturon metabolite was detected. The study thus shows that the fungal pathways differ from the bacterial pathways and yield new metabolites of possible environmental concern.