Determination of potential sources of PCBs and PBDEs in sediments of the Niagara River

Sediments from Niagara River, an important waterway connecting two of the Great Lakes (Lake Erie to Lake Ontario), were analyzed for 14 congeners of polychlorinated biphenyls (PCBs) and 9 congeners of polybrominated diphenyl ethers (PBDEs) using accelerated solvent extraction and gas chromatography/mass spectrometry. Total concentrations of PCBs ranged from 1.7 to 124.6 ng/g were PCBs 138 and 153 were found in all samples. All sites but one showed PBDE in sediments with total concentrations as high as 148 ng/g, suggesting that PBDE is becoming an important class of POP. A land-use and coverage map was used to trace potential localized sources of PCB and PBDE contamination. Results indicate that the highest levels of PCBs and PBDEs were found in sediments collected from areas closest to the discharge locations of municipal wastewater treatment plants (WWTP) and local industries. This is the first study that suggests the importance of WWTP discharges as a potential source of PBDE contamination in the Great Lakes.     

The Best-of-2-Worlds philosophy: Developing local dismantling and global infrastructure network for sustainable e-waste treatment in emerging economies

E-waste is a complex waste category containing both hazardous and valuable substances. It demands for a cost-efficient treatment system which simultaneously liberates and refines target fractions in an environmentally sound way. In most developing countries there is a lack of systems covering all steps from disposal until final processing due to limited infrastructure and access to technologies and investment. This paper introduces the ‘Best-of-2-Worlds’ philosophy (Bo2W), which provides a network and pragmatic solution for e-waste treatment in emerging economies. It seeks technical and logistic integration of ‘best’ pre-processing in developing countries to manually dismantle e-waste and ‘best’ end-processing to treat hazardous and complex fractions in international state-of-the-art end-processing facilities. A series of dismantling trials was conducted on waste desktop computers, IT equipment, large and small household appliances, in order to compare the environmental and economic performances of the Bo2W philosophy with other conventional recycling scenarios. The assessment showed that the performance of the Bo2W scenario is more eco-efficient than mechanical separation scenarios and other local treatment solutions. For equipment containing substantial hazardous substances, it demands the assistance from domestic legislation for mandatory removal and safe handling of such fractions together with proper financing to cover the costs. Experience from Bo2W pilot projects in China and India highlighted key societal factors influencing successful implementation. These include market size, informal competitors, availability of national e-waste legislation, formal take-back systems, financing and trust between industrial players. The Bo2W philosophy can serve as a pragmatic and environmentally responsible transition before establishment of end-processing facilities in developing countries is made feasible. The executive models of Bo2W should be flexibly differentiated for various countries by adjusting to local conditions related to operational scale, level of centralized operations, dismantling depth, combination with mechanical processing and optimized logistics to international end-processors.     

Earthworm additions affect leachate production and nitrogen losses in typical midwestern agroecosystems

Earthworms affect soil structure and the movement of agrochemicals. Yet, there have been few field-scale studies that quantify the effect of earthworms on dissolved nitrogen fluxes in agroecosystems. We investigated the influence of semi-annual earthworm additions on leachate production and quality in different row crop agroecosystems. Chisel-till corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotation (CT) and ridge-till corn-soybean-wheat (Triticum aestivum L.) rotation (RT) plots were arranged in a complete randomized block design (n = 3) with earthworm treatments (addition and ambient) as subplots where zero-tension lysimeters were placed 45 cm below ground. We assessed earthworm populations semi-annually and collected leachate biweekly over a three-year period and determined leachate volume and concentrations of total inorganic nitrogen (TIN) and dissolved organic nitrogen (DON). Abundance of deep-burrowing earthworms was increased in addition treatments over ambient and for both agroecosystems. Leachate loss was similar among agroecosystems, but earthworm additions increased leachate production in the range of 4.5 to 45.2% above ambient in CT cropping. Although leachate TIN and DON concentrations were generally similar between agroecosystems or earthworm treatments, transport of TIN was significantly increased in addition treatments over ambient in CT cropping due to increased leachate volume. Losses of total nitrogen in leachate loadings were up to approximately 10% of agroecosystem N inputs. The coincidence of (i) soluble N production and availability and (ii) preferential leaching pathways formed by deep-burrowing earthworms thereby increased N losses from the CT agroecosystem at the 45-cm depth. Processing of N compounds and transport in soil water from RT cropping were more affected by management phase and largely independent of earthworm activity.     

Biological monitoring of aromatic diisocyanates in workers exposed to thermal degradation products of polyurethanes

Exposure to diisocyanates was assessed by biological monitoring among workers exposed to the thermal degradation products of polyurethanes (PURs) in five PUR-processing environments. The processes included grinding and welding in car repair shops, milling and turning of PUR-coated metal cylinders, injection moulding of thermoplastic PUR, welding and cutting of PUR-insulated district heating pipes during installation and joint welding, and heat-flexing of PUR floor covering. Isocyanate-derived amines in acid-hydrolysed urine samples were analysed as perfluoroacylated derivatives by gas chromatography mass spectrometry in negative chemical ionisation mode. The limits of quantification (LOQs) for the aromatic diamines 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA) and 4,4'-methylenedianiline (4,4'-MDA) were 0.25 nmol l(-1), 0.25 nmol l(-1) and 0.15 nmol l(-1), respectively. The LOQ for the aliphatic diamines hexamethylenediamine (HDA), isophoronediamine (IpDA) and 4,4'-diaminodicyclohexyl methane (4,4'-DDHM) was 5 nmol l(-1). TDA and MDA were detected in urine samples from workers in car repair shops and MDA in samples from workers welding district heating pipes. The 2,4-TDA isomer accounted for about 80% of the total TDA detected. No 2.6-TDA was found in the urine of non-exposed workers. The highest measured urinary TDA and MDA concentrations were 0.79 nmol mmol(-1) creatinine and 3.1 nmol mmol(-1) creatinine, respectively. The concentrations found among non-exposed workers were 0.08 nmol mmol(-1) creatinine for TDA and 0.05 nmol mmol(-1) creatinine for MDA (arithmetic means). Exposure to diisocyanates originating from the thermal degradation of PURs are often intermittent and of short duration. Nevertheless, exposure to aromatic diisocyanates can be identified by monitoring diisocyanate-derived amines in acid-hydrolysed urine samples.     

Monitoring priority substances of directives 76/464/EEC and 2000/60/EC in Greek water bodies

The priority substances of List I, 76/464/EEC Directive, some of which belong to the new Water Framework Directive 2000/60/EC, have been monitored in the surface waters of Greece through the developed network of 53 sampling stations. The analytical methods used for the determination of these substances included Purge and Trap-Gas chromatography-Mass spectrometry for volatile and semivolatile organic compounds, Gas Chromatography-Electron Capture Detection for organochlorine insecticides, High Performance Liquid Chromatography for pentachlorophenol and Atomic Absorption Spectrometry for metals. The results have shown the presence of several priority substances in Greek surface waters, in most cases at concentrations well below the regulatory limits. However, non-compliance was observed for a limited number of compounds. The monitoring network and the analytical determinations have to be expanded to more water bodies and more priority substances, in order to safeguard the quality of Greek surface waters.     

Effervescence assisted dispersive liquid–liquid microextraction followed by microvolume UV-Vis spectrophotometric determination of surfactants in water

The novel and simple methods for the sensitive determination of cationic and anionic surfactants in water based on effervescence assisted dispersive liquid–liquid microextraction and microvolume UV-Vis spectrophotometry have been developed. The method involves ion-pair extraction of cationic and anionic surfactants with organic dyes (methyl orange and azure A, respectively) during the dispersion of extraction solvent (CHCl₃) by CO₂ bubbles which are formed by the injection of a mixture of the extraction solvent and proton donor solvent into the sample solution which contains carbonate-ions as effervescency agent. The analytical performance of the proposed procedure was compared with the conventional dispersive liquid–liquid microextraction. Appropriate experimental conditions for both methods were investigated. The absorbances of the colored extracts at wavelengths of 440 and 625 nm obey Beer's law within the range of 0.1–5.0 mg/L for both cationic and anionic surfactants. The limit of detection (LOD) obtained using the effervescence assisted extraction method was 30 µg/L for cationic and anionic surfactants. The proposed methods were successfully applied to determination of surfactants in water samples.     

Photodegradation of the antibiotic spiramycin studied by high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry

The degradation of spiramycin induced by ultraviolet (UV) irradiation was studied at pH 3–4, 6–7 and 8–9 using high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry. Furthermore, the influence of hydrogen peroxide and oxygen on the photodegradation was investigated. Three degradation products were observed in the presence of oxygen and four in the absence of oxygen. The degradation kinetics were monitored as mass area-time curves, analyzed and described using subsequent follow-up reaction first-order models. The m/z values of the degradation products were determined to be 160, 322 and 366, the latter representing two separate products, the sugar moieties of spiramycin. Remainders of the macrocycle or the intact lactone ring of spiramycin were not observed, since the conjugated π-electron system was assumed photoexcited and thus undergoing photodegradation and fast destruction of the ring. The kinetic of the degradation of spiramycin itself was described using a first-order model. The degradation was accelerated upon addition of hydrogen peroxide. In contrast, systematic acceleration depending on pH could not be found. The absence of oxygen did not lead to any significant acceleration. The findings are interpreted in terms of the effectiveness of advanced oxidation processes and their potential use as a fourth purification step in wastewater treatment plants.     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.