Mass Spectrometric Detection and Identification of Polar Pesticides and their Degradation Products - A Comparison of Different Ionization Methods

Due to increasing use of polar pesticides, they are found together with their degradation products in ground- and surface waters serving for drinking water treatment. The triazine derivatives acetamido-atrazine, ametryne, atrazine, cyanazine, deethylatrazine, deethyldeisopropyl-hydroxyatrazine, deethyl-hydroxyatrazine, deisopropyl-atrazin, deisopropyl-hydroxyatrazine, desmetryn, hydroxyatrazine, prometryne, propazine, simazine, terbumeton, terbutryne and terbutylazine, and the pesticides 2,4-D, dichlorprop, isoproturon, diuron, metolachlor, glyphosate, metsulfuronmethyl and dalapon, all of them belonging to this type of pesticides, have been studied. For determination of triazine derivatives UV detection by means of diode array detector (DAD) as well as mass spectrometric (MS) detection coupled by thermospray interface (TSP) have been used successfully after liquid chromatoraphic (LC) separation. Interfaces like thermospray (TSP), electrospray (ESP) and atmospheric pressure chemical ionisation (APCI) were examined with regard to their suitability for substance-specific detection of polar pesticides by flow injection analysis (FIA) with MS- and tandem mass spectroscopic detection (MS/MS) without preceding LC separation. Optimised detection conditions for these pesticides using FIA are presented, and solutions for occurring problems are offered.     

Investigating phosphorus limitation in a fixed bed filter with phosphorus and nitrogen profile measurements

In 2000, the European Union adopted the European Water Framework Directive (WFD) (European Commission, 2000). The WFD focuses on increasingly stringent nutrient standards including ultra low nitrogen (< 2.2 mg N-total/L) and phosphorus concentrations (< 0.15 mg total phosphorus/L) in receiving surface waters and in relevant point sources like wastewater treatment plant (WWTP) effluent. Expansion of WWTPs with advanced post-treatment processes, like effluent filtration, is widely proposed to meet possible future effluent discharge standards. When combining biological nitrate-nitrogen and chemical phosphorus removal in one filter, phosphorus limitation in the denitrifying process may occur. This study investigated where in the filter bed and under which conditions phosphorus limitation occurs. Profile measurements for nitrate, nitrite, and orthophosphorus (PO4-P) combined with chemical oxygen demand (COD) and 02 were conducted. Results showed that the required PO4-P/NOx-N ratio is approximately 0.006 mg/mg after phosphorous precipitation and flocculation. Profile measurements have proven to be an applicable and useful tool. It showed how nitrate and orthophosphorus are removed through the filter bed based on the PO4-P/NOx-N ratio. When orthophosphorus is removed more rapidly and efficiently compared to nitrate, the PO4-P/NOx-N ratio decreases. When PO4-P/NOx-N ratio thresholds are approximately 0.006 mg/mg for a certain period of time and water temperatures varied significantly, orthophosphorus limitation may occur. Changing the filter-bed configuration or decreasing the coagulant dosage can prevent limitation of the denitrifying process because of a phosphorous shortage.     

Exposure to toxic waste containing high concentrations of hydrogen sulphide illegally dumped in Abidjan, C?te d’Ivoire

Introduction

On August 2006, a cargo ship illegally dumped 500?t of toxic waste containing high concentrations of hydrogen sulphide in numerous sites across Abidjan. Thousands of people became ill. Seventeen deaths were associated with toxic waste exposure.

Materials and methods

This study reports on environmental and health problems associated with the incident. A cross-sectional transect study was conducted in five waste dumping site areas.

Results

Of the households, 62.1% (n?=?502) were exposed to the effects of the pollutants and 51.1% of the interviewed people (n?=?2,368) in these households showed signs of poisoning. Most important symptoms were cough (37.1%), asthenia (33.1%), pruritus (29.9%) and nausea (29.1%).

Discussion

The health effects showed different frequencies in the five waste impact sites. Among the poisoned persons, 21.1% (n?=?532) presented symptoms on the survey day (i.e., 4?months after incident). Transect sampling allowed to determine a radius of vulnerability to exposure of up to 3?km from the point of toxic waste disposal.

Conclusion

The area of higher vulnerability is influenced by various environmental factors, such as size and severity of pollution site, duration of toxic waste pollution on the impact site and locally climatic conditions. The surveillance of effects on environment and human health is warranted to monitor the development.     

Blood serum concentrations of perfluorinated compounds in men from Greenlandic Inuit and European populations

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are used in large quantities. They are persistent and found in measurable levels in human serum around the world. They have been associated with developmental, hepatic, and carcinogenic effects in animal studies. The aim of the present study was to describe levels of PFCs in serum among Inuits from Greenland and inhabitants from Warsaw, Poland and Kharkiv, Ukraine. Furthermore, the aim was to define social- and lifestyle related determinants of exposure for these compounds. Serum levels of seven PFCs were analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentrations of PFOS and PFOA were the highest of all PFCs in all three populations with a total amount of almost 90% of the PFCs. The mean levels of PFOS and PFOA were in the Greenlandic Inuits 52 and 4.8 ng mL(-1), in Poland 19 and 5.2 ng mL(-1), and in Ukraine 8.1 and 1.9 ng mL(-1), respectively. Thus, levels of PFCs in the serum of Inuits on Greenland were among the highest described in a general population whereas the levels in Poland were similar to other industrialized countries. The exposure in Ukraine was rather low. In the Greenlandic Inuit population, intake of seafood, tea, age and area of living were significant determinants of PFOS concentrations and explained about 22% of the variation. For the other populations no strong determinants were found.     

Prevention of struvite scaling in digesters combined with phosphorus removal and recovery--the FIX-Phos process

The fixation of phosphorus (FIX-Phos) combines struvite prevention and phosphorus recovery by the addition of calciumsilicatehydrate (CSH) particles into the anaerobic digester. The CSH fixates phosphorus as calcium phosphate and reduces the phosphorus concentration in the sludge water that allows for control of struvite formation. The phosphorus-containing recovery product can be separated and recovered from the digested sludge. In pilot plant experiments, 21% to 31% of phosphorus contained in digested sludge could be recovered when CSH was added at concentrations of 2 g/L to 3.5 g/L to a mixture of primary sludge and waste activated sludge (WAS) from enhanced biological phosphorus removal. The recovery product contained few heavy metals and a phosphorus content of 18 wt % P2O5, which allows for recycling as fertilizer. The fixation of phosphorus within the digester may increase wastewater sludge dewaterability. The phosphorus recycle stream to the headworks of the wastewater treatment plant is reduced.     

How should support for climate-friendly technologies be designed?

Stabilizing global greenhouse gas concentrations at levels to avoid significant climate risks will require massive "decarbonization" of all the major economies over the next few decades, in addition to the reduced emissions from other GHGs and carbon sequestration. Achieving the necessary scale of emissions reductions will require a multifaceted policy effort to support a broad array of technological and behavioral changes. Change on this scale will require sound, well-thought-out strategies. In this article, we outline some core principles, drawn from recent social science research, for guiding the design of clean technology policies, with a focus on energy. The market should be encouraged to make good choices: pricing carbon emissions and other environmental damage, removing distorting subsidies and barriers to competition, and supporting RD&D broadly. More specific policies are required to address particular market failures and barriers. For those technologies identified as being particularly desirable, some narrower RD&D policies are available.     

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.     

Acceleration of the Fe(III)EDTA(-) reduction rate in BioDeNO(x) reactors by dosing electron mediating compounds

BioDeNO(x), a novel technique to remove NO(x) from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N(2). Besides NO reduction, high rate biological Fe(III)EDTA(-) reduction is a crucial factor for a succesful application of the BioDeNO(x) technology, as it determines the Fe(II)EDTA(2-) concentration in the scrubber liquor and thus the efficiency of NO removal from the gas phase. This paper investigates the mechanism and kinetics of biological Fe(III)EDTA(-) reduction by unadapted anaerobic methanogenic sludge and BioDeNO(x) reactor mixed liquor. The influence of different electron donors, electron mediating compounds and CaSO(3) on the Fe(III)EDTA(-) reduction rate was determined in batch experiments (21mM Fe(III)EDTA(-), 55 degrees C, pH 7.2+/-0.2). The Fe(III)EDTA(-) reduction rate depended on the type of electron donor, the highest rate (13.9mMh(-1)) was observed with glucose, followed by ethanol, acetate and hydrogen. Fe(III)EDTA(-) reduction occurred at a relatively slow (4.1mMh(-1)) rate with methanol as the electron donor. Small amounts (0.5mM) of sulfide, cysteine or elemental sulfur accelerated the Fe(III)EDTA(-) reduction. The amount of iron reduced significantly exceeded the amount that can be formed by the chemical reaction of sulfide with Fe(III)EDTA(-), suggesting that the Fe(III)EDTA(-) reduction was accelerated via an auto-catalytic process with an unidentified electron mediating compound, presumably polysulfides, formed out of the sulfur additives. Using ethanol as electron donor, the specific Fe(III)EDTA(-) reduction rate was linearly related to the amount of sulfide supplied. CaSO(3) (0.5-100mM) inhibited Fe(III)EDTA(-) reduction, probably because SO(3)(2-) scavenged the electron mediating compound.     

Establishment of a constructed wetland in extreme dryland

Background, aim, and scope

The project was set to construct an extensive wetland in the southernmost region of Israel at Kibbutz Neot Smadar (30°02′45″ N and 35°01′19″ E). The results of the first period of monitoring, summary, and perspectives are presented. The constructed wetland (CW) was built and the subsequent monitoring performed in the framework of the Southern Arava Sustainable Waste Management Plan, funded by the EU LIFE Fund. The specific aims were: (1) To end current sewage disposal and pollution of the ground, the aquifer, and the dry river bed (wadi) paths by biologically treating the sewage as part of the creation of a sustainable wetland ecosystem. (2) Serve as an example of CW in the Negev highlands and the Arava Valley climates for neighboring communities and as a test ground for plants and building methods appropriate to hyper arid climate. (3) Serve as an educational resource and tourist attraction for groups to learn about water reuse, recycling, local wildlife and migrating birds, including serving the heart of a planned Ecological–Educational Bird Park. This report is intended to allow others who are planning similar systems in hyper arid climates to learn from our experience.

Materials and methods

The project is located in an extreme arid desert with less than 40 mm of rain annually and temperature ranges of ?5°C to +42°C. The site receives 165–185 m³ of municipal and agricultural wastes daily, including cowshed and goat wastes and winery outflow.

Results

The CW establishment at Neot Smadar was completed in October 2006. For 8 months, clean water flowed through the system while the plants were taking root. In June 2007, the wetland was connected to the oxidation pond and full operation began. Because of seepage and evaporation, during the first several months, the water level was not high enough to allow free flow from one bed to the next. To bed A, the water was pumped periodically from the oxidation pond (Fig. 1) and from there flowed by gravitation through the rest of the system. The initial results of the monitoring are promising. In nearly all measurements, the system succeeded as expected to reduce levels of contaminants at least to the level acceptable for irrigating fruit trees and often to the level of unlimited irrigation. The introduction of the plants in the system and their physiological performance were evaluated and were found to correlate well to the quality of water in the various beds.

Discussion

It should be said at the outset that evaluation of the performance of a CW system is a long-term process. Thus, the main aim of this report is to present the problems, difficulties, preliminary results, and concepts concerned with the first stage of establishment of CW in an extremely dry region.

Conclusions

The CW system was designed to dispose of municipal and agricultural wastes in a way that not merely reduces pollution, but adds to environmental quality by creating accessible parkland for local residents and tourists. Several factors affected the performance of the system at the initial stages of operation: ecological balance between microbes and plants, big seasonal variations, seepage and evaporation reduced the flow in the initial operation of the system. Despite the initial difficulties, the quality of water coming out the system is acceptable for irrigation.

Recommendations and perspectives

The CW can function well under extreme dryland conditions. The oxidation pond was the major source of evaporation and bad odors. Therefore, alternatives to the oxidation pond are needed. Cost effectiveness of the system still has to be evaluated systematically.     

The bibliometrics of atmospheric environment

Bibliometric analysis is an important tool in the management of a journal. SCOPUS output is used to assess the increase in the quantity of material in Atmospheric Environment and stylistic changes in the way authors choose words and punctuation in titles and assemble their reference lists. Citation analysis is used to consider the impact factor of the journal, but perhaps more importantly the way in which it reflects the importance authors give to papers published in Atmospheric Environment. The impact factor of Atmospheric Environment (2.549 for 2007) from the Journal Citation Reports suggests it performs well within the atmospheric sciences, but it conceals the long term value authors place on papers appearing in the journal. Reference lists show that a fifth come through citing papers more than a decade old.