Entry and toxicity of organic pesticides and copper in vineyard streams: Erosion rills jeopardise the efficiency of riparian buffer strips

The present study was performed to characterise in-stream pesticide exposure within the Palatinate vineyard region in south-west Germany, evaluate the influence of buffer strip widths and identify mitigation measures for the relevant entry pathways. In-stream water and sediment samples that were taken at nine sampling sites of different buffer widths following intense rainfall, and edge-of-field runoff that were sampled in erosion rills were analysed regarding 28 active ingredients of pesticides including copper. In-stream samples contained a mix of 8 ± 4 pesticide compounds, resulting in total pesticide concentrations of 1.4-8.9 μg l⁻¹ for water and 16-670 μg kg⁻¹ dw for sediment. Following an exceptional rainfall event with a previous 34-day drought period, pesticide concentrations reached 7.0-83.4 μg l⁻¹. Fungicides were the most important pesticides found and were significantly correlated with the pesticide application frequency and rate. The calculated toxicity values per sample (TU_max) indicated that both organic pesticides and copper concentrations likely cause ecotoxicological effects in the field. The buffer strip width was of little importance for pesticide in-stream concentrations because pesticide entry occurred mainly via the field path network and erosion rills. Pesticide in-stream concentrations were significantly and positively correlated with the concentrations detected in erosion rills (R² = 0.56). As possible risk mitigation measures, we suggest the implementation of grassed field paths and vegetated ditches or wetlands.     

Forecasting the e ects of EU policy measures on the nitrate pollution of groundwater and surface waters

We used the interdisciplinary model network REGFLUD to predict the actual mean nitrate concentration in percolation water at the scale of the Weser river basin (Germany) using an area di erentiated (100 m 100 m) approach. REGFLUD combines the agro-economic model RAUMIS for estimating nitrogen surpluses and the hydrological models GROWA/DENUZ for assessing the nitrate leaching from the soil. For areas showing predicted nitrate concentrations in percolation water above the European Union (EU) groundwater quality standard of 50 mg NO3-N/L, e ective agri-environmental reduction measures need to be derived and implemented to improve groundwater and surface water quality by 2015. The e ects of already implemented agricultural policy are quantified by a baseline scenario projecting the N-surpluses from agricultural sector to 2015. The REGFLUD model is used to estimate the e ects of this scenario concerning groundwater and surface water pollution by nitrate. From the results of the model analysis the needs for additional measures can be derived in terms of required additional N-surplus reduction and in terms of regional prioritization of measures. Research work will therefore directly support the implementation of the Water Framework Directive of the European Union in the Weser basin.     

Forecasting the effects of EU policy measures on the nitrate pollution of groundwater and surface waters

We used the interdisciplinary model network REGFLUD to predict the actual mean nitrate concentration in percolation water at the scale of the Weser river basin (Germany) using an area differentiated (100 m × 100 m) approach.REGFLUD combines the agro-economic model RAUMIS for estimating nitrogen surpluses and the hydrological models GROWA/DENUZ for assessing the nitrate leaching from the soil.For areas showing predicted nitrate concentrations in percolation water above the European Union (EU) groundwater quality standard of 50 mg NO 3 -N/L,effective agri-environmental reduction measures need to be derived and implemented to improve groundwater and surface water quality by 2015.The effects of already implemented agricultural policy are quantified by a baseline scenario projecting the N-surpluses from agricultural sector to 2015.The REGFLUD model is used to estimate the effects of this scenario concerning groundwater and surface water pollution by nitrate.From the results of the model analysis the needs for additional measures can be derived in terms of required additional N-surplus reduction and in terms of regional prioritization of measures.Research work will therefore directly support the implementation of the Water Framework Directive of the European Union in the Weser basin.     

Determination of polyfluoroalkyl compounds in water and suspended particulate matter in the river Elbe and North Sea, Germany

The distribution of polyfluoroalkyl compounds (PFCs) in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied. The PFCs quantified included C₄-C₈ perfluorinated sulfonates (PFSAs), 6:2 fluorotelomer sulfonate (6:2 FTS), C₆ and C₈ perfluorinated sulfinates (PFSiAs), C₄-C₁₂ perfluorinated carboxylic acids (PFCAs), perfluoro-3,7-dimethyl-octanoic acid (3,7m₂-PFOA), perfluorooctane sulfonamide (FOSA), and n-ethyl perfluroctane sulfonamidoethanol (EtFOSE). PFCs were mostly distributed in the dissolved phase, where perfluorooctanoic acid (PFOA) dominated with 2.9–12.5 ng/L. In the suspended particulate matter FOSA and perfluorooctane sulfonate (PFOS) showed the highest concentrations (4.0 ng/L and 2.3 ng/L, respectively). The total flux of ΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase. This indicates that the river Elbe acts as a source of PFCs into the North Sea. However, the concentrations of perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) in the North Sea were higher than that in the river Elbe, thus an alternative source must exist for these compounds.     

Remote sampling of a CO2 point source in an urban setting

High frequency CO₂ and wind speed measurements were used to examine the urban baseline eddy covariance CO₂ flux and analyse the CO₂ rich plume from a local power station. A reliable relationship between high frequency CO₂ maxima and the rate of CO₂ emission at the power station was established. This relationship was shown to be highly dependant on wind speed. The ensemble mean plume was found to be Gaussian in horizontal profile with a width dependant on wind speed. The relationship between peak CO₂ mixing ratio and averaging time was shown to be a simple power law with a time exponent of approximately 0.5. The large, short pulses in CO₂ mixing ratio in the power plant plume were found to have an approximately Lorentzian shape. These pulses generated negative vertical eddy flux measurements so data from the plume sector were necessarily excluded from the flux baseline results. The plume-excluded flux had a similar magnitude and variability to those reported in other urban CO₂ flux studies despite this site not being ideal due to the proximity of roughness elements to the measurement point.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Misuse of null hypothesis significance testing: would estimation of positive and negative predictive values improve certainty of chemical risk assessment?

Although generally misunderstood, the p value is the probability of the test results or more extreme results given H₀ is true: it is not the probability of H₀ being true given the results. To obtain directly useful insight about H₀, the positive predictive value (PPV) and the negative predictive value (NPV) may be useful extensions of null hypothesis significance testing (NHST). They provide information about the probability of statistically significant and non-significant test outcomes being true based on an a priori defined biologically meaningful effect size. The present study explores the utility of PPV and NPV in an ecotoxicological context by using the frequently applied Daphnia magna reproduction test (OECD guideline 211) and the chemical stressor lindane as a model system. The results indicate that especially the NPV deviates meaningfully between a test design strictly following the guideline and an experimental procedure controlling for α and β at the level of 0.05. Consequently, PPV and NPV may be useful supplements to NHST that inform the researcher about the level of confidence warranted by both statistically significant and non-significant test results. This approach also reinforces the value of considering α, β, and a biologically meaningful effect size a priori.     

Mental health outcomes of job stress among Chinese teachers: role of stress resource factors and burnout

This study examined the mental health outcomes of job stress among Chinese teachers in Hong Kong. A total of 269 Chinese teachers participated in Study 1 which provided cross‐sectional data regarding the associations among stress resource factors, burnout, and negative mental health. Study 2 was a six‐month longitudinal study which aimed to establish the direction of the associations among the hypothesized variables across two time points with a separate sample of 61 Chinese secondary school teachers. Results of the structural equation modelling analyses on the cross‐sectional data at T1 showed that stress resource factors of self‐efficacy and proactive attitude were negatively related to burnout, which in turn had a direct effect on negative mental health. Stress resource factors were also directly linked to mental health status of teachers. Results of similar analyses on the longitudinal data at T2 further indicated that burnout at T1 had a direct impact on burnout at T2, which in turn had a direct effect on negative mental health at T2. Findings and limitations of the study were discussed. Copyright © 2001 John Wiley & Sons, Ltd.