Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

Load Acceleration and Footstep Strategies in Asymmetrical Lifting and Lowering

Accelerated execution effects for lifting and lowering a 12-kg box using two footstep strategies associated with experienced workers were studied. Eight healthy male participants performed a normal and an accelerated execution of a lifting task and a lowering task, using a minimal feet displacement strategy (oblique-step) and a strategy with a step (crossed-step). It was hypothesized that the accelerated executions, as compared to the normal executions, would have a different effect on L5/S1 resultant moment, body posture, and other kinematic variables. A tridimensional dynamic rigid body model was used to compute L5/S1 resultant moments. Results showed that the accelerated condition did not reduce body asymmetry of posture, but it reduced the length of the path of the global center of gravity and the duration of the supporting phase of the box, and it did not significantly affect L5/S1 maximal resultant moments for lifting but increased them for lowering. These results indicate that the net work production for accelerated strategies might be smaller, which may represent an economy of energy. Furthermore, the results showed that the use of an accelerated strategy for lowering should be avoided.     

Levels of major organochlorine contaminants in sequentially - laid Herring Gull eggs

Sequentially laid eggs of Herring Gulls in Lake Erie and the Detroit River (Ontario) were found to contain increasingly higher levels of organochlorine contaminants. The reason for this was not determined but a depletion of lipid pools during the egg laying period and a rapid equilibrium between body and egg burdens may explain the results. It is recommended that, for long term toxic residue monitoring, eggs at the same position in the order of laying be taken from all sampled clutches.     

The International Drinking Water Supply and Sanitation Decade in retrospect and implications for the future

In global terms this paper reviews the progress made during the International Drinking Water Supply and Sanitation Decade. There has been considerable progress. In terms of percent receiving water services, the urban areas made good progress: 77% in 1980 to 82% in 1990. In the rural areas progress was even greater, 30% had water services in 1980 versus 63% in 1990. There was also considerable progress in institutional terms. A positive trend towards better linkage betweeen authorities dealing with water supply and sanitation and those dealing with economic development, was one. Another was the awareness of the need for community involvement. In some cases progress was hampered by fragmentation of governmental authorities dealing with water and sanitation at the rural and/or urban level. In the 1990s an important issue will be financing the infrastructure needed to bring water and sanitation services to those not already covered and to an increasing population. Institutional issues will continue to be important as well.     

Second generation anticoagulant rodenticides in predatory birds: Probabilistic characterisation of toxic liver concentrations and implications for predatory bird populations in Canada

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent pests but exposure and poisonings occur in non-target species, such as birds of prey. Liver residues are often analysed to detect exposure in birds found dead but their use to assess toxicity of SGARs is problematic. We analysed published data on hepatic rodenticide residues and associated symptoms of anticoagulant poisoning from 270 birds of prey using logistic regression to estimate the probability of toxicosis associated with different liver SGAR residues. We also evaluated exposure to SGARs on a national level in Canada by analysing 196 livers from great horned owls (Bubo virginianus) and red-tailed hawks (Buteo jamaicensis) found dead at locations across the country. Analysis of a broader sample of raptor species from Quebec also helped define the taxonomic breadth of contamination. Calculated probability curves suggest significant species differences in sensitivity to SGARs and significant likelihood of toxicosis below previously suggested concentrations of concern (<0.1mg/kg). Analysis of birds from Quebec showed that a broad range of raptor species are exposed to SGARs, indicating that generalised terrestrial food chains could be contaminated in the vicinity of the sampled areas. Of the two species for which we had samples from across Canada, great horned owls are exposed to SGARs to a greater extent than red-tailed hawks and the liver residue levels were also higher. Using our probability estimates of effect, we estimate that a minimum of 11% of the sampled great horned owl population is at risk of being directly killed by SGARs. This is the first time the potential mortality impact of SGARs on a raptor population has been estimated.     

Does intensity of change matter? Factors affecting adoption of agri-environmental schemes in Spain

Agri-environmental schemes (AES) are the main policy instrument currently available in the EU to promote environmentally-friendly farming practices. However, the rate of adoption of these measures is still relatively low in southern Europe, and understanding how these rates can be increased is still an open issue. The goal of this paper is to increase that understanding by testing whether the factors which determine AES sign-up decisions are influenced by the intensity of change in farming practices that are brought about by adopting the scheme. A micro-economic model reflecting farmer AES sign-up decisions is proposed and applied to two schemes in Spain respectively requiring major or minor intensity of change in practices by surveying farmers eligible for both schemes. The results show that farm structural factors play a role when major practice change is required by the scheme, yet when dealing with minor change, individual farmer characteristics play a more determining role. Social capital and farmer attitude are important factors in both the AES surveyed. Therefore, it may be concluded that improving agronomic design would be an important tool to improve farmer participation in AES where major change is involved, whereas improved targeting and extension would help uptake for AES involving a lesser degree of change.     

Characterization of summertime coarse particulate matter in the Desert Southwest—Arizona,USA

A year-long study was conducted in Pinal County, AZ, to characterize coarse (2.5 – 10 μm aerodynamic diameter, AD) and fine (< 2.5 μm AD) particulate matter (PMc and PMf, respectively) to further understand spatial and temporal variations in ambient PM concentrations and composition in rural, arid environments. Measurements of PMc and PMf mass, ions, elements, and carbon concentrations at one-in-six day resolution were obtained at three sites within the region. Results from the summer of 2009 and specifically the local monsoon period are presented.

The summer monsoon season (July – September) and associated rain and/or high wind events, has historically had the largest number of PM₁₀ NAAQS exceedances within a year. Rain events served to clean the atmosphere, decreasing PMc concentrations resulting in a more uniform spatial gradient among the sites. The monsoon period also is characterized by high wind events, increasing PMc mass concentrations, possibly due to increased local wind-driven soil erosion or transport. Two PM₁₀ NAAQS exceedances at the urban monitoring site were explained by high wind events and can likely be excluded from PM₁₀ compliance calculations as exceptional events. At the more rural Cowtown site, PM₁₀ NAAQS exceedances were more frequent, likely due to the impact from local dust sources.

PM mass concentrations at the Cowtown site were typically higher than at the Pinal County Housing and Casa Grande sites. Crustal material was equal to 52-63% of the PMc mass concentration on average. High concentrations of phosphate and organic carbon found at the rural Cowtown were associated with local cattle feeding operations. A relatively high correlation between PMc and PMf (R²?=?0.63) indicated that the lower tail of the coarse particle fraction often impacts the fine particle fraction, increasing the PMf concentrations. Therefore, reductions in PMc sources will likely also reduce PMf concentrations, which also are near the value of the 24-hr PM_2.5 NAAQS.

Implications: In the desert southwest, summer monsoons are often associated with above average PM₁₀ (<10 μm AD) mass concentrations. Competing influences of monsoon rain and wind events showed that rain suppresses ambient concentrations while high wind increase them. In this region, the PMc fraction dominates PM₁₀ and crustal sources contribute 52-63% to local PMc mass concentrations on average. Cattle feedlot emissions are also an important source and a unique chemical signature was identified for this source. Observations suggest monsoon wind events alone cannot explain PM₁₀ NAAQS exceedances, thus requiring these values to remain in compliance calculations rather than being removed as exceptional wind events.     

Wood Smoke Contribution to Winter Aerosol in Fresno,CA

Abstract

In an effort to better quantify wintertime particulate matter (PM) and the contribution of wood smoke to air pollution events in Fresno, CA, a field campaign was conducted in winter 2003–2004. Coarse and fine daily PM samples were collected at five locations in Fresno, including residential, urban, and industrial areas. Measurements of collected samples included gravimetric mass determination, organic and elemental carbon analysis, and trace organic compound analysis by gas chromatograph mass spectrometry (GC/MS). The wood smoke tracer levoglucosan was also measured in aqueous aerosol extracts using high-performance anion exchange chromatography coupled with pulsed amperometric detection. Sample preparation and analysis by this technique is much simpler and less expensive than derivatized levoglucosan analysis by GC/MS, permitting analysis of daily PM samples from all five of the measurement locations. Analyses revealed low spatial variability and similar temporal patterns of PM_2.5 mass, organic carbon (OC), and levoglucosan. Daily mass concentrations appear to have been strongly influenced by meteorological conditions, including precipitation, wind, and fog events. Fine PM (PM_2.5) concentrations are uncommonly low during the study period, reflecting frequent precipitation events. During the first portion of the study, levoglucosan had a strong relationship to the concentrations of PM_2.5 and OC. In the later portion of the study, there was a significant reduction in levoglucosan relative to PM_2.5 and OC. This may indicate a change in particle removal processes, perhaps because of fog events, which were more common in the latter period. Combined, the emissions from wood smoke, meat cooking, and motor vehicles appear to contribute ~65–80% to measured OC, with wood smoke, on average, accounting for ~41% of OC and ~18% of PM_2.5 mass. Two residential sites exhibit somewhat higher contributions of wood smoke to OC than other locations.