Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths <60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.     

Temperature and water pressure head effects on the degradation of the diketonitrile metabolite of isoxaflutole in a loamy soil under two tillage systems

Laboratory studies were conducted to evaluate the effects of temperature and water pressure head on the degradation of the diketonitrile metabolite (DKN) of isoxaflutole during 84 d in samples collected in a loamy soil under conventional (CT) and conservation (MT) tillage systems. Soil temperature was the major factor controlling DKN degradation in the two tillage systems. The shortest half-lives (T_1/2) were measured in the seedbed samples under MT at 25 °C and −33 cm water pressure head. We found that mouldboard ploughing under CT was responsible for the spatial variability of herbicide degradation properties, whereas under MT herbicide degradation was associated to the vertical distribution of organic matter.     

Long term changes in atmospheric N and S throughfall deposition and effects on soil solution chemistry in a Scots pine forest in the Netherlands

In a Scots pine forest the throughfall deposition and the chemical composition of the soil solution was monitored since 1984. (Inter)national legislation measures led to a reduction of the deposition of nitrogen and sulphur. The deposition of sulphur has decreased by approximately 65%. The total mineral-nitrogen deposition has decreased by ca. 25%, which is mainly due to a reduction in ammonium-N deposition (−40%), since nitrate-N deposition has increased (+50%). The nitrogen concentration in the upper mineral soil solution at 10 cm depth has decreased, leading to an improved nutritional balance, which may result in improved tree vitality. In the drainage water at 90 cm depth the fluxes of NO₃⁻ and SO₄²⁻ have decreased, resulting in a reduced leeching of accompanying base cations, thus preserving nutrients in the ecosystem. It may take still several years, however, before this will meet the prerequisite of a sustainable ecosystem.     

Remediation of copper-contaminated topsoils from a wood treatment facility using in situ stabilisation

Five organic matters, three phosphate compounds, zerovalent iron grit (ZVIG, 2% by soil weight), two alkaline compounds, and two commercial formulations were incorporated, singly and some combined with ZVIG, into a highly Cu-contaminated topsoil (Soil P7, 2600 mg Cu kg⁻¹) from a wood treatment facility. Formulations and two composts were also singly incorporated into a slightly Cu-contaminated topsoil (Soil P10, 118 mg Cu kg⁻¹) from the facility surrounding. This aimed to reduce the labile pool of Cu and its accumulation in beans cultivated on potted soils in a climatic chamber. Lowest Cu concentration in soil solution occurred in P7 soils amended with activated carbon (5%) and ZVIG, singly and combined. Basic slag (3.9%) and compost of sewage sludge (5%) combined with ZVIG promoted shoot production and limited foliar Cu accumulation. For amended P10 soils, no changes occurred in soil solution and foliar Cu concentrations, but one compost increased shoot production.     

Characterization of the toxic effects of cadmium and 3.5-dichlorophenol on nitrifying activity and mortality in biologically activated sludge systems—effect of low temperature

Background, aims, and scope  Sometimes, urban wastewaters convey a more or less significant part of toxic products from industries or the craft industry. Nitrifying activity can be affected by these substances, implying higher ammonia concentrations in the outlet effluent and contributing to toxicity for the aquatic environment. Moreover, the more stringently treated wastewater standards now require a reliable treatment for nitrogen. One of the key issues is the identification of the inhibition behavior of nitrifying bacteria facing a toxic substance. This new understanding could then finally be integrated into models in order to represent and to optimize wastewater treatment plants (WWTP) operation in cases involving ‘toxic scenarios’. Materials and methods  The toxic substances studied in this work, cadmium and 3.5-dichlorophenol (3.5-DCP), are representative of chemical substances commonly found in municipal sewage and industrial effluents and symbolize two different contaminant groups. The effects of Cd and 3.5-DCP on nitrification kinetics have been investigated using respirometry techniques. Results  IC50 values determination gives concentrations of 3.1 mg/L for 3.5-DCP and 45.8 mg/L for Cd at 21 ± 1°C. The variation to low temperature seems to have no real effect on IC50 for DCP, but induces a decrease of cadmium IC50 to 27.5 mg/L at 14°C. Finally, specific respirometric tests have been carried out in order to determine the potential effect of these toxic substances on the nitrifying decay rate b _a . No significant effect has been noticed for Cd, whereas the presence of 3.5-DCP (at IC50 concentration) induced a dramatic increase of b _a at 20°C. The same behavior has been confirmed by experiments performed in winter periods with a sludge temperature around 12°C. Discussion  The target substances have different modes of action on activity and mortality, notably due to the abilities of the contaminant to be precipitated, accumulated, or even to be progressively degraded. Studies realized at low temperature confirmed this assumption, and put in evidence the effect of temperature on toxic substances capable of being biosorbed. However, the change in the sludge sample characteristics can be pointed out as a problem in the investigation of the temperature effect on nitrification inhibition, as biosorption, bioaccumulation, and predation are directly linked to the sludge characteristics (VSS concentration, temperature) and the plant operating conditions (loading rates, sludge age, etc.). Conclusions  This work brings new understandings concerning the action mode of these specific contaminants on nitrifying bacteria and, in particular, on the role of temperature. The experiments lead to the determination of the IC50 values for both toxic substances on biological nitrification. The inhibition mechanisms of Cd and 3.5-DCP on nitrifying activity have been simply represented by a non-competitive inhibition model. Recommendations and perspectives  Other experiments carried out in a continuous lab-scale pilot plant should be done with a proper control of the operating conditions and of the sludge characteristics in order to better understand the mechanisms of nitrification inhibition for each contaminant. Finally, these first results show that toxic substances can have an effect on the growth rate but also on the decay rate, depending on the characteristics of the toxic substance and the sludge. This eventual double effect would imply different strategies of WWTP operation according to the behavior of the contaminant on the bacteria.     

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.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Acute toxic hazard evaluations of glyphosate herbicide on terrestrial vertebrates of the oregon coast range

GOAL, SCOPE AND BACKGROUND: The degree to which dose responses of model organisms (lab rodents) can adequately predict dose responses of free-ranging wild mammals or amphibians is unknown, and the relative sensitivity of such species to body loading of a toxicant such as glyphosate is seldom reported. For relative effects of dosage, we compare sensitivity of nine wild vertebrate species to effects of high doses of glyphosate in Swiss-Webster laboratory mice both by gavage and by intraperitoneal injection. We also evaluate sublethal effects of herbicide exposure on behavior and reproductive success of one mammal and one amphibian species. METHODS: Comparisons of acute toxicity of glyphosate were made with intraperitoneal dosings of technical glyphosate isopropylamine salt to nine species of terrestrial vertebrates (five amphibians, four mammals) and compared with responses in Swiss-Webster laboratory mice. Animals collected from sites that had no recent herbicide application were allowed 7-14 days to equilibrate in captivity before treatment. RESULTS: Median lethal dose ranged from 800 to 1,340 mg kg(-1) in mammals, and 1,170 to >2,000 mg kg(-1) in amphibians, with Oregon vole being the most sensitive. White lab mice were in the middle of the mammalian range. Tailed frog, at >2,000 mg kg(-1) was the least sensitive. Calibration of IP sensitivity to oral administration by gavage indicated that roughly four times as much glyphosate must be administered to obtain a comparable estimate of lethality. Administration by gavage in highly concentrated solutions tended to cause physical injury, hence may prove less useful as a relative indicator of toxicity. When sublethal dosages were given to roughskin newts or chipmunks, mobility and use of cover appeared largely unaffected. DISCUSSION: Direct toxic effects of spraying glyphosate under normal forest management seem unlikely for the nine species examined. Nor could we detect significant indirect effects of exposure on behavior and use of cover features in two species. There may be effects on other aspects of the field biology of these animals, such as reproductive rates, which we did not investigate. Recent field data indicate that changes in habitat quality following herbicide application can result in high reproductive activity in species associated with the grasses and forbs that proliferate following field applications. CONCLUSIONS: When compared to field data on body burdens of wild mammals exposed after aerial application of glyphosate at maximum rates in forests, there seems to be a large margin of safety between dosages encountered and those causing either death or limitation of movement, foraging or shelter. RECOMMENDATIONS AND PERSPECTIVES: Margins of safety for small mammals and amphibians appear to be large under any probable exposure scenarios, however our results indicate high variability in responses among species. Uncertainty introduced into field studies from unknown sources of mortality (e.g, likely predation) must be considered when interpreting our results.