Elimination of racemic and enantioenriched metalaxyl based fungicides under tropical conditions in the field

The elimination has been studied of racemic and enantioenriched metalaxyl applied as an emulsifiable concentrate and wettable powder combined with copper in a Cameroonian field site. The kinetics of the degradation/dissipation of metalaxyl and its acid metabolite were investigated using reversed phase HPLC-MS/MS, while the enantiomeric ratios were measured by HPLC-MS/MS using a Chiralcel OD-H HPLC column. Some soil enzymes activities were determined concurrently for 120d. The elimination of racemic metalaxyl was shown to be enantioselective, with the R-enantiomer being degraded more slowly than the S-enantiomer. Dissipation followed approximate square root first-order kinetics (R>0.98) without lag phases. The enantiomers of metalaxyl have different elimination rates, with half-lives ranging from only 0.8 to 1.5 days. After application to soil, the elimination of metalaxyl in the copper containing formulation was slower. The activities of acid phosphatase, alkaline phosphatase, and alkaline glucosidase were monitored throughout the experiments. No significant influence of metalaxyl and copper could be observed on these parameters. The significantly shorter half-life values of all forms of metalaxyl under field conditions, compared to the previously reported laboratory derived ones, may have implications for the plant disease control with these fungicides in tropical rainforest areas.     

Predicting community sensitivity to ozone, using Ellenberg Indicator values

This paper develops a regression-based model for predicting changes in biomass of individual species exposed to ozone (RS(p)), based on their Ellenberg Indicator values. The equation (RS(p)=1.805-0.118Light-0.135 square root Salinity) underpredicts observed sensitivity but has the advantage of widespread applicability to almost 3000 European species. The model was applied to grassland communities to develop two further predictive tools. The first tool, percentage change in biomass (ORI%) was tested on data from a field-based ozone exposure experiment and predicted a 27% decrease in biomass over 5 years compared with an observed decrease of 23%. The second tool, an index of community sensitivity to ozone (CORI), was applied to 48 grassland communities and suggests that community sensitivity to ozone is primarily species-driven. A repeat-sampling routine showed that nine species were the minimum requirement to estimate CORI within 5%.     

Development of microbial degradation of cypermethrin and diazinon in organically and conventionally managed soils

The behaviour of pesticides in the soil is a complex issue and is controlled by the physical, chemical and biological properties of the soil. The ability of microorganisms to degrade pesticides is not only controlled by the bioavailability of a chemical but also by their capacity to develop the ability to utilise available chemicals. The development of catabolism in the indigenous soil microflora of four organically and one conventionally managed soils was investigated for two pesticides: cypermethrin and diazinon. Soils were amended with cypermethrin and diazinon and aged for 0, 2, 4, 6, 8, and 14 weeks and, at each time point, mineralisation of freshly added 14C-cypermethrin or 14C-diazinon was measured by trapping 14CO2. In general, contact times between the soil and the pesticide resulted in a reduction in the lag phase (the period of time before mineralisation exceeded 5% of the added activity), followed by increases in the extent of mineralisation. Cypermethrin was mineralised significantly in all soils; whereas, diazinon was only appreciably mineralised in two of the soils, most notably in the organic soil from Redesdale. Statistical analysis showed pH and organic matter content of the soil had a significant effect on the extent of mineralisation (P< or = 0.05) of the cypermethrin in the soils.     

Polycyclic aromatic hydrocarbons (PAHs) in the air of Chinese cities

Polycyclic aromatic hydrocarbons (PAHs) were determined in the air of 37 cities and 3 rural locations across China during the winter, spring, summer and autumn of 2005, using polyurethane foam (PUF) disks as passive air samplers (PAS). Winter and autumn concentrations in cities exceeded spring and summer values. Concentrations were amongst the highest in the world; seasonally averaged autumn/winter values in some cities in the north and north-west of China exceeded proposed European Union air quality standards. Several factors, acting in combination, influenced air concentrations. A significant negative correlation was found between average annual city concentrations and the annual average temperature, while winter time PAH concentrations correlated with estimated coal consumption. The highest total PAH concentrations and loadings of high molecular weight compounds generally occurred in major cities located on higher land (500-2000 m), where relatively cold winters and higher coal consumption occurs. Lower values occurred in cities located in the south and east China and along the coastal regions. Molecular markers indicated incomplete combustion of fossil fuels dominated the urban air and gave evidence for photo-decomposition of selected compounds.     

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Troms?, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.     

Human dietary intake of organochlorines from Baltic herring: implications of individual fish variability and fisheries management

This study examines the extent to which Finnish human dietary intake of organochlorines (PCDD/Fs and PCBs) originating from Northern Baltic herring can be influenced by fisheries management. This was investigated by estimation of human intake using versatile modeling tools (e.g., a herring population model and a bioenergetics model). We used a probabilistic approach to account for the variation in human intake of organochlorines originating from the variation among herring individuals. Our estimates were compared with present precautionary limits and recommendation for use. The results show that present consumption levels and frequencies of herring give a high probability of exceeding recommended intake limits of PCDD/Fs and PCBs. Furthermore, our results clearly demonstrate that in the risk management of dioxinlike organochlorines, regulating fishing (in this case increasing fishing pressure) is a far less effective way to decrease the risk than regulating the consumption of herring. Increased fishing would only slightly decrease organochlorine concentrations of herring in the Finnish fish market.     

Sediment quality triad assessment of an industrialized estuary of the northeastern USA

The lower Passaic River in northern New Jersey (USA) has been heavily industrialized since the mid-nineteenth century and its shoreline and aquatic habitats degraded or destroyed. Similar to other urban systems, Passaic River sediments, both surface and buried, historically have contained elevated levels of numerous contaminants that may pose risks to ecological receptors and humans. Sediments from 15 stations in the lower Passaic River and 3 reference stations in the Mullica River in southern New Jersey were sampled in 1999 and characterized for chemical contamination, toxicity, and impairment of the benthic community. The objective of this study was to determine the incidence, degree, and nature of degraded surficial sediments in the area to support subsequent plans for restoration of the system. Results demonstrated that Passaic River sediments had concentrations of many organic and inorganic contaminants at levels significantly greater than the reference area and effect-based guidelines. Sediments were toxic to marine amphipods at 11 stations and the benthic assemblages were impaired relative to the reference area at all stations. The weight-of-evidence of this sediment quality triad (SQT) assessment indicates that impacts from multiple contaminants are occurring throughout the lower Passaic River and, that these impacts must be evaluated further and addressed as part of ongoing restoration initiatives for the river.     

Fish abundances in shoreline habitats and submerged aquatic vegetation in a tidal freshwater embayment of the Potomac River

Submerged aquatic vegetation (SAV) is considered an important habitat for juvenile and small forage fish species, but many long-term recruitment surveys do not effectively monitor fish communities in SAV. To better understand the impact of recent large increases of SAV on the fish community in tidal freshwater reaches of the Potomac River, we compared traditional seine sampling from shore with drop ring sampling of SAV beds (primarily Hydrilla) in a shallow water (depths, <1.5 m) embayment, Gunston Cove. To accomplish this, we developed species-specific catch efficiency values for the seine gear and calculated area-based density in both shoreline and SAV habitats in late summer of three different years (2007, 2008, and 2009). For the dominant species (Fundulus diaphanus, Lepomis macrochirus, Etheostoma olmstedi, Morone americana, Lepomis gibbosus, and Fundulus heteroclitus), density was nearly always higher in SAV, but overall, species richness was highest in shoreline habitats sampled with seines. Although historical monitoring of fish in Gunston Cove (and throughout Chesapeake Bay) is based upon seine sampling (and trawl sampling in deeper areas), the high densities of fish and larger areal extent of SAV indicated that complementary sampling of SAV habitats would produce more accurate trends in abundances of common species. Because drop ring samples cover much less area than seines and may miss rare species, a combination of methods that includes seine sampling is needed for biodiversity assessment. The resurgence of SAV in tidal freshwater signifies improving water quality, and methods we evaluated here support improved inferences about population trends and fish community structure as indicators of ecosystem condition.     

Revisiting the Chesapeake Bay Phytoplankton Index of Biotic Integrity

In 2006, a phytoplankton index of biotic integrity (PIBI) was published for Chesapeake Bay Lacouture et al. (Estuaries 29(4):598–616, 2006). The PIBI was developed from data collected during the first 18 years (1985–2002) of the Chesapeake Bay Program long-term phytoplankton and water quality monitoring programs. Combinations of up to nine phytoplankton metrics were selected to characterize bay habitat health according to plankton community condition in spring and summer seasons across four salinity zones. The independent data available at the time for index validation was not sufficient to test the PIBI because they lacked critical index parameters (pheophytin and dissolved organic carbon) and reference samples for some seasons and salinity zones. An additional 8 years of monitoring data (2003–2010) are now available to validate the original index, reassess index performance and re-examine long-term trends in PIBI conditions in the Bay. The PIBI remains sensitive to changes in nutrient and light conditions. Evaluation of the PIBI results over the entire 1985–2010 time period shows no discernible trends in the overall health of Bay habitat based on phytoplankton community conditions. This lack of overall PIBI trend appears to be a combined response to declines in water clarity and improvements in dissolved inorganic nitrogen and dissolved phosphorus conditions in the bay.     

Application of a Life Cycle Simulation Model to Evaluate Impacts of Water Management and Conservation Actions on an Endangered Population of Chinook Salmon

Fisheries and water resource managers are challenged to maintain stable or increasing populations of Chinook salmon in the face of increasing demand on the water resources and habitats that salmon depend on to complete their life cycle. Alternative management plans are often selected using professional opinion or piecemeal observations in place of integrated quantitative information that could reduce uncertainty in the effects of management plans on population dynamics. We developed a stochastic life cycle simulation model for an endangered population of winter-run Chinook salmon in the Sacramento River, California, USA with the goal of providing managers a tool for more effective decision making and demonstrating the utility of life cycle models for resource management. Sensitivity analysis revealed that the input parameters that influenced variation in salmon escapement were dependent on which age class was examined and their interactions with other inputs (egg mortality, Delta survival, ocean survival). Certain parameters (river migration survival, harvest) that were hypothesized to be important drivers of population dynamics were not identified in sensitivity analysis; however, there was a large amount of uncertainty in the value of these inputs and their error distributions. Thus, the model also was useful in identifying future research directions. Simulation of variation in environmental inputs indicated that escapement was significantly influenced by a 10% change in temperature whereas larger changes in other inputs would be required to influence escapement. The model presented provides an effective demonstration of the utility of life cycle simulation models for decision making and provides fisheries and water managers in the Sacramento system with a quantitative tool to compare the impact of different resource use scenarios.