Regulation (EC) No. 1107/2009 and upcoming challenges for exposure assessment of plant protection products--Harmonisation or national modelling approaches?

In the new European Pesticide Regulation (EC) No. 1107/2009, the harmonisation of approaches for estimation of the environmental exposure of pesticides is considered a major goal. Several member states currently require their own models for the calculation of predicted environmental concentrations (PEC) in surface water. The variety of methods makes risk evaluations rather time-consuming for both notifiers and evaluating authorities. In the present study we compare surface water concentrations of 19 compounds using EU and country-specific models and risk assessment approaches to evaluate to which extent the resulting estimated exposure concentrations differ. Our results show that EU and country specific approaches and the resulting surface water concentrations differ considerably regarding basic model assumptions and assessment methods. The results indicate that the aimed harmonisation of risk assessment approaches within the EU will be difficult based on current models. New scenarios may help to achieve a harmonisation taking country-specific features into account.     

Photophysical and photochemical properties of the pharmaceutical compound salbutamol in aqueous solutions

Salbutamol is a potent β₂-adrenergic receptor agonist widely used in the treatment of bronchial asthma and chronic obstructive pulmonary disease. An increasing number of studies have detected salbutamol in natural water systems worldwide. Studies have shown that sunlight degrades salbutamol resulting in the formation of products; some showing higher toxicity to bacteria Vibrio fischeri than the parent compound. In this contribution, steady-state absorption and emission techniques, high-performance liquid chromatography, and transient absorption spectroscopy are used to investigate the photochemistry of salbutamol in aqueous buffer solutions at controlled pH values. Ground- and excited-state calculations that include solvent effects are performed to guide the interpretation of the experimental results. Salbutamol is sensitive to UVB light absorption in the pH range from 3 to 12, forming products that absorb light at longer wavelengths than the parent compound. Quantum yields of degradation reveal that the deprotonated species is 10-fold more photo-active than the protonated species. In line with this result, the fluorescence quantum yield of the protonated species is more than an order of magnitude higher than that of the deprotonated species. Transient absorption spectroscopy shows that population of the triplet state occurs with a rate constant of 7.1 × 10⁸ s⁻¹ in the protonated species, while a rate constant of 1.7 × 10¹⁰ s⁻¹ is measured for the deprotonated species. While degradation of the deprotonated species is not affected by the presence of molecular oxygen, a twofold increase in the photodegradation yield of the protonated species in air-saturated conditions is observed.     

Spatial and seasonal variations in atrazine and metolachlor surface water concentrations in Ontario (Canada) using ELISA

Concerns regarding the impacts of pesticides on aquatic species and drinking water sources have increased demands on water quality monitoring programs; however the costs of sample analysis can be prohibitive. In this study we investigated enzyme-linked immunosorbent assay (ELISA) as a cost-effective, high through-put method for measuring pesticide concentrations in surface waters. Seven hundred and thirty-nine samples from 158 locations throughout Ontario were analysed for atrazine and metolachlor from April to October 2007. Concentrations ranged from <0.1 to 3.91 μg L⁻¹ (median = 0.12 μg L⁻¹) for atrazine and from <0.1 to 1.83 μg L⁻¹ (median = 0.09 μg L⁻¹) for metolachlor. Peak concentrations occurred in late spring/early summer, in rural agricultural locations, and decreased over the remainder of the growing season for both herbicides. About 3% of the samples that had ELISA results occurring above the limit of quantification (0.10 μg L⁻¹) were evaluated against gas chromatography-mass spectrometry (GC-MS). Linear regression analysis revealed a R² value of 0.88 and 0.39, for atrazine and metolachlor, respectively. ELISA tended to overestimate concentrations for atrazine and metolachlor, most likely because the ELISA kits also detect their metabolites. Atrazine data suggest that ELISA may be used complementary with GC-MS analysis to enhance the spatial and temporal resolution of a water quality monitoring study. The commercially available metolachlor ELISA kit requires further investigation. ELISA may be used to detect atrazine and metolachlor in surface water samples, but it is not recommended as a quantitative replacement for traditional analytical methods.     

Watershed factors affecting stream acidification in the White Mountains of New Hampshire,USA

The streams tributary to acidic Cone Pond, pH 4.5–4.8, and circumneutral Black Pond, pH 5.3–6.4, in the White Mountains of New Hampshire, USA, were monitored for a year. The watersheds of these two ponds were characterized in terms of geology and stream hydrology. Chemical gradients and patterns in rock weathering and groundwater discharge explain many of the differences in mineral content and acidity of the streams. The rocks of Black watershed produced an average of ten times the equivalent of basic cations as rocks from Cone watershed. This is on the same order as the difference in acidity of the two streams. Down-stream changes in stream chemistry follow differing patterns, but reflect the same principle of residence time and water path length controlling chemical evolution of streamwater. Watershed and aquatic managers may use these parameters in an inexpensive and simple assessment of the susceptibility of individual streams and ponds to acidification. A method is recommended to determine quickly the potential influence of bedrock type to aquatic chemistry.     

SENSITIVITY OF HIGH-ELEVATION STREAMS IN THE SOUTHERN BLUE RIDGE PROVINCE TO ACIDIC DEPOSITION1

ABSTRACT: The Southern Blue Ridge Province, which encompasses parts of northern Georgia, eastern Tennessee, and western North Carolina, has been predicted to be sensitive to impacts from acidic deposition, owing to the chemical composition of the bedrock geology and soils. This study confirms the predicted potential sensitivity, quantifies the level of total alkalinity and describes the chemical characteristics of 30 headwater streams of this area. Water chemistry was measured five times between April 1983 and June 1984 at first and third order reaches of each stream during baseflow conditions. Sensitivity based on total alkalinity and the Calcite Saturation Index indicates that the headwater streams of the Province are vulnerable to acidification. Total alkalinity and p11 were generally higher in third order reaches (mean, 72 μeq/θ and 6.7) than in first order reaches (64 μeq/θ and 6.4). Ionic concentrations were low, averaging 310 and 340 μeq/θ in first and third order reaches, respectively. A single sampling appears adequate for evaluating sensitivity based on total alkalinity, but large temporal variability requires multiple sampling for the detection of changes in pH and alkalinity over time. Monitoring of stream water should continue in order to detect any subtle effects of acidic deposition on these unique resource systems.     

地面水中叶枯灵的高效液相色谱测定

本文采用反相高效液相色谱法，在质控条件下，对河水，塘水两种地面水中叶枯灵的检验方法进行了测试，用Shimapck ODS柱为分析柱，以甲醇：水＝50：50为流动相，并用冰醋酸调PH至4－5，紫外检测波长281nm，两种水样的平均回收率分别为91．7－96．3％，90－95．8％，相对标准偏差为4．3％，最低检出限为0．0261mg/l，为地面水中叶枯灵卫生标准的实施提供了简便，灵敏，正确的配套测试手段。     

COMPARATIVE WATER CHEMISTRY OF FOUR LAKES IN ROCKY MOUNTAIN NATIONAL PARK1

ABSTRACT: The inorganic chemistry of two pairs of lakes in Rocky Mountain National Park was studied to determine reasons for their similarities and differences. The pairs were located on differing geologic units. It was expected that weathering from the different types of parent material would cause differing cation concentrations between the pairs. This was verified by dissimilar concentrations of those cations which are products of primary weathering. Unexpected was a significant difference in anion concentrations between members of one pair having the same bedrock geology. This difference has been attributed to the presence of a wet sedge meadow above one of the lakes which serves as a biological filter for anions, particularly nitrate and sulfate. It is shown that small scale drainage characteristics which can alter regional atmospheric contributions are important contributors to lake chemistry.     

Patterns of Streamwater Acidity in Lye Brook Wilderness,Vermont, USA

Under the United States Clean Air Act Amendments of 1977, a class I designation safeguards wilderness areas from the negative effects of new sources of air pollution. We monitored streamwater chemistry in the class I Lye Brook Wilderness in southwestern Vermont from May 1994 through August 1995. Stream samples were collected biweekly at nine sampling locations throughout the wilderness and were analyzed for major cations and anions, dissolved organic carbon, pH, and acid-neutralizing capacity. Eight of nine sites sampled had mean annual acid neutralizing capacity values below zero. During the study period, decreases in streamwater acid neutralizing capacity values were caused primarily by SO₄ ²⁻. At some sites, however, NO₃ ⁻ and naturally occurring, weak organic acids were seasonally important. During high discharge, the low pH and high concentrations of inorganic monomeric Al were at levels that are toxic to acid-sensitive aquatic species. Watershed mass balances were calculated to determine annual gains or losses for measured ions. These budgets indicate that S inputs and outputs were nearly equal, there was a net loss of base cations, and a net gain in N. How long these watersheds can continue to assimilate additional N inputs is unknown.     

Chemical Changes in Sediment Pore-Waters of an Acidic Mining Lake After Addition of Organic Substrate and Lime for Stimulating Lake Remediation

In the past five years, enclosures have beeninstalled in an acidic mining lake in Lusatia to investigate insitu remediation processes. They were treated with straw, withstraw and Carbokalk, or with Carbokalk alone, where Carbokalkis a by-product of the sugar industry (solid precipitate ofnon-sugars after lime clarification of extracted sugar beetjuice). Sediment samples were taken as cores to get informationabout the behaviour of organic and inorganic components insediment pore-water with depth. Vertical distributions of pH,soluble reactive phosphate, nitrate, ammonium, silica,aluminium, iron, manganese, calcium, magnesium, sodium,potassium, sulphate, and DOC were measured. The resultingprofiles, each consisting of 15 data points at differentdepths, were compared by cluster analysis. The similarities ofsediment cores from different treated enclosures relating toprofiles of chemical components were discussed. Increasedconcentrations of potassium and sulphate were found in pore-water after substrate treatment. The data imply dissolution ofpotassium iron sulphate hydroxide minerals (jarosite) after anincrease of pH caused by dissolution of lime and by sulphatereducing processes which were stimulated by organic substrateaddition.