Review of advances in the thin layer chromatography of pesticides: 2004-2006

Applications of thin layer chromatography and high performance thin layer chromatography for the separation, detection, and qualitative and quantitative determination of pesticides, other agrochemicals, and related compounds are reviewed for the period from July 1, 2004 to November 1, 2006. Analyses are covered for a variety of samples, such as food, crops, biological, environmental, pharmaceuticals, and formulations, and for residues of pesticides of various types, including insecticides, herbicides, and fungicides, belonging to different chemical classes. In addition to references on residue analysis, studies such as pesticide-structure relationships, metabolism, degradation, and lipophilicity are covered, many of which make use of thin layer radiochromatography.     

Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.     

Assessment and comparison of the environmental performances of a regional incinerator network

In Emilia-Romagna region (Northern Italy) the integrated waste treatment system consists of material collection and recycling, incineration with energy recovery and landfill as final disposal. In particular, at least one incineration plant is working in almost every province of the region. In this work, a screening life cycle assessment approach is applied to seven different incinerators, to compare the different plant technologies and identify the most relevant environmental impacts and processes. The characterization method used in the life cycle impact assessment step is Eco-indicator 99. The functional unit is 1 ton of waste input. As a first result, it can be noted that while the combustion systems are rather similar, the main variables are ascribable to gas cleaning options and efficiency in energy recovery, which result in quite different environmental performances. Among heavy metals, particular attention must be paid to Cd and As, due to their high toxicity, despite their low quantities. The impact due to dioxin emission is orders of magnitude lower than other contaminants (e.g., heavy metals). Furthermore, a catalytic system could be useful for a complete removal of organic contaminants and for a more effective abatement of nitrogen oxides. Finally, the environmental impact assessment sorts the various plants according to their age, i.e., the most recent plants provide the best environmental performances for the same quantity of combusted waste.     

Status of the Riparian Ecosystem in the Upper San Pedro River, Arizona: Application of an Assessment Model

A portion of Arizona’s San Pedro River is managed as a National Riparian Conservation Area but is potentially affected by ground-water withdrawals beyond the conservation area borders. We applied an assessment model to the Conservation Area as a basis for monitoring long-term changes in riparian ecosystem condition resulting from changes in river water availability, and collected multi-year data on a subset of the most sensitive bioindicators. The assessment model is based on nine vegetation bioindicators that are sensitive to changes in surface water or ground water. Site index scores allow for placement into one of three condition classes, each reflecting particular ranges for site hydrology and vegetation structure. We collected the bioindicator data at 26 sites distributed among 14 reaches that had similar stream flow hydrology (spatial flow intermittency) and geomorphology (channel sinuosity, flood-plain width). Overall, 39% of the riparian corridor fell within condition class 3 (the wettest condition), 55% in condition class 2, and 6% in the driest condition class. Condition class 3 reaches have high cover of herbaceous wetland plants (e.g., Juncus and Schoenoplectus spp.) along the perennial stream channel and dense, multi-aged Populus-Salix woodlands in the flood plain, sustained by shallow ground water in the stream alluvium. In condition class 2, intermittent stream flows result in low cover of streamside wetland herbs, but Populus-Salix remain abundant in the flood plain. Perennial wetland plants are absent from condition class 1, reflecting highly intermittent stream flows; the flood plain is vegetated by Tamarixa small tree that tolerates the deep and fluctuating ground water levels that typify this reach type. Abundance of herbaceous wetland plants and growth rate of Salix gooddingii varied between years with different stream flow rates, indicating utility of these measures for tracking short-term responses to hydrologic change. Repeat measurement of all bioindicators will indicate long-term trends in hydro-vegetational condition.     

Supervisor expediency to employee expediency: The moderating role of leader–member exchange and the mediating role of employee unethical tolerance

We utilize social learning theory to test the role‐modeling effect of supervisor expediency (i.e., a supervisor's use of unethical practices to expedite work for self‐serving purposes). In particular, we examine the relationship between supervisor expediency and employee expediency, as moderated by leader–member exchange (LMX) and mediated by employee unethical tolerance. We predict that employees are more likely to model their supervisors' expedient behaviors when their relationship is characterized by high‐LMX (a high‐quality exchange relationship that is rich in socioemotional support). Furthermore, we argue that supervisor expediency, especially when LMX is high, influences employees' attitudes of unethical tolerance, which then affects employees' expedient behaviors. Across 2 multisource field studies and a third time‐lagged field study, we found general support for our theoretical predictions. Theoretical and practical implications are discussed.     

Will photosynthetic capacity of aspen trees acclimate after long-term exposure to elevated CO2 and O3?

Photosynthetic acclimation under elevated carbon dioxide (CO₂) and/or ozone (O₃) has been the topic of discussion in many papers recently. We examined whether or not aspen plants grown under elevated CO₂ and/or O₃ will acclimate after 11 years of exposure at the Aspen Face site in Rhinelander, WI, USA. We studied diurnal patterns of instantaneous photosynthetic measurements as well as A/C_i measurements monthly during the 2004-2008 growing seasons. Our results suggest that the responses of two aspen clones differing in O₃ sensitivity showed no evidence of photosynthetic and stomatal acclimation under either elevated CO₂, O₃ or CO₂ + O₃. Both clones 42E and 271 did not show photosynthetic nor stomatal acclimation under elevated CO₂ and O₃ after a decade of exposure. We found that the degree of increase or decrease in the photosynthesis and stomatal conductance varied significantly from day to day and from one season to another.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

Air pollutants and health outcomes: Assessment of confounding by influenza

We assessed confounding of associations between short-term effects of air pollution and health outcomes by influenza using Hong Kong mortality and hospitalization data for 1996–2002.Three measures of influenza were defined: (i) intensity: weekly proportion of positive influenza viruses, (ii) epidemic: weekly number of positive influenza viruses ≥4% of the annual number for ≥2 consecutive weeks, and (iii) predominance: an epidemic period with co-circulation of respiratory syncytial virus <2% of the annual positive isolates for ≥2 consecutive weeks. We examined effects of influenza on associations between nitrogen dioxide (NO₂), sulfur dioxide (SO₂), particulate matter with aerodynamic diameter ≤10 μm (PM₁₀) and ozone (O₃) and health outcomes including all natural causes mortality, cardiorespiratory mortality and hospitalization. Generalized additive Poisson regression model with natural cubic splines was fitted to control for time-varying covariates to estimate air pollution health effects. Confounding with influenza was assessed using an absolute difference of >0.1% between unadjusted and adjusted excess risks (ER%).Without adjustment, pollutants were associated with positive ER% for all health outcomes except asthma and stroke hospitalization with SO₂ and stroke hospitalization with O₃. Following adjustment, changes in ER% for all pollutants were <0.1% for all natural causes mortality, but >0.1% for mortality from stroke with NO₂ and SO₂, cardiac or heart disease with NO₂, PM₁₀ and O₃, lower respiratory infections with NO₂ and O₃ and mortality from chronic obstructive pulmonary disease with all pollutants. Changes >0.1% were seen for acute respiratory disease hospitalization with NO₂, SO₂ and O₃ and acute lower respiratory infections hospitalization with PM₁₀. Generally, influenza does not confound the observed associations of air pollutants with all natural causes mortality and cardiovascular hospitalization, but for some pollutants and subgroups of cardiorespiratory mortality and respiratory hospitalization there was evidence to suggest confounding by influenza.     

New Approaches to the Design of Afterburners for Varnish Cookers

The best method of controlling varnish kettle emissions is by thermal incineration. Two new approaches have been developed; these utilize the integral-blower burner and the non-powered raw gas burner. Both of these new approaches offer significant advantages over conventional methods of incineration. Installation, operating, and maintenance costs are substantially reduced when either approach is utilized.

When compared to conventional methods, the new approaches achieve an increase of 100% in mixing velocity or turbulence. This results in a reduction of 20% in fuel consumption. Residence time is reduced by 29% via the non-powered raw gas burner approach. An average reduction of 65% is obtained in the length to diameter ratio. Choice of which approach depends upon several factors, primarily the type of fuel available and the minimum oxygen concentration in the fume stream.