Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

Sustainability, substance flow management and time. Part I Temporal analysis of substance flows

Flows of chemical substances need to be managed in a sustainable way. Sustainable development as a whole and the sustainable management of substance flows in particular are both time issues. These include the importance of the dynamics of substance flows and the way these interconnect with the use of resources, the avoidance of environmental pollution, and their effects on health and food production. Another prerequisite for the proper management of substance flows is justice within and between generations. This requires a systematic approach and a systematic analysis of the issues as well as of the actions to be taken. One tool for such a systematic approach is temporal analysis. It brings the temporal aspects of the substances themselves and of their intended use, as well as factors affecting the stakeholders, such as decision makers, producers and consumers, into focus. In the past, timing factors were rarely taken into account. Knowledge of the temporal dynamics of substance flows and their resultant outcomes, as well as of their interaction with ecological, economic and social systems, is a basic requirement for successful substance flow management. The need to include temporal aspects into substance flow management and how to do so is outlined here. Included are not only politicians but also practitioners and scientists who must explicitly take into account adequate time scales, points in time, breaks and other forms of time in planning and acting.     

Model approach for estimating potato pesticide bioconcentration factor

We presented a model that estimates the bioconcentration factor (BCF) of pesticides in potatoes supposing that the pesticide in the soil solution is absorbed by the potato by passive diffusion, following Fick's second law. The pesticides in the model are nonionic organic substances, traditionally used in potato crops that degrade in the soil according to a first-order kinetic equation. This presents an expression that relates BCF with the pesticide elimination rate by the potato, with the pesticide accumulation rate within the potato, with the rate of growth of the potato and with the pesticide degradation rate in the soil. BCF was estimated supposing steady state equilibrium of the quotient between the pesticide concentration in the potato and the pesticide concentration in the soil solution. It is suggested that a negative correlation exists between the pesticide BCF and the soil sorption partition coefficient. The model was built based on the work of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108], in which an expression to calculate the diffusivity of persistent organic substances in potatoes is presented. The model consists in adding to the expression of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108] the hypothesis that the pesticide degrades in the soil. The value of BCF suggests which pesticides should be monitored in potatoes.     

Characteristics and assessment of phthalate esters in urban dusts in Guangzhou city, China

Phthalate esters (PAEs) were examined in indoor and outdoor dust samples from the subtropical city of Guangzhou, China. The ∑(16)PAEs concentrations ranged from 121 to 3,223 μg g(-1) dust, with the median concentration of 840 μg g(-1) dust. Significantly higher concentrations of PAEs in dust samples were found in offices where electrical and electronic devices, carpet pads, and office furniture were widely used. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in indoor and outdoor dust samples, and accounted for >96.8% and >93.1% of the ∑(16)PAEs concentrations, respectively. The median daily inhalation exposure of ∑(16)PAEs were 3.53 and 0.247 μg kg(-1) body weight day(-1), and at the 95(th) percentile were 7.62 and 0.530 μg kg(-1) body weight day(-1), up on the measured concentrations and estimated dust ingestion rates, respectively, for toddles and adults. The ubiquitous distribution of PAEs as noted in this study suggests the need for detailed assessment of PAEs concentrations using more sites and to further investigate the factors influencing PAEs exposure in China.     

Integrated approach for demarcating subsurface pollution and saline water intrusion zones in SIPCOT area: a case study from Cuddalore in Southern India

This paper deals with a systematic hydrogeological, geophysical, and hydrochemical investigations carried out in SIPCOT area in Southern India to demarcate groundwater pollution and saline intrusion through Uppanar River, which flows parallel to sea coast with high salinity (average TDS 28, 870 mg/l) due to back waters as well as discharge of industrial and domestic effluents. Hydrogeological and geophysical investigations comprising topographic survey, self-potential, multi-electrode resistivity imaging, and water quality monitoring were found the extent of saline water intrusion in the south and pockets of subsurface pollution in the north of the study area. Since the area is beset with highly permeable unconfined quaternary alluvium forming potential aquifer at shallow depth, long-term excessive pumping and influence of the River have led to lowering of the water table and degradation of water quality through increased salinity there by generating reversal of hydraulic gradient in the south. The improper management of industrial wastes and left over chemicals by closed industries has led surface and subsurface pollution in the north of the study area.     

Characterizing the intrinsic bioremediation potential of 1,4-dioxane and trichloroethene using innovative environmental diagnostic tools

An intrinsic biodegradation study involving the design and implementation of innovative environmental diagnostic tools was conducted to evaluate whether monitored natural attenuation (MNA) could be considered as part of the remedial strategy to treat an aerobic aquifer contaminated with 1,4-dioxane and trichloroethene (TCE). In this study, advanced molecular biological and stable isotopic tools were applied to confirm in situ intrinsic biodegradation of 1,4-dioxane and TCE. Analyses of Bio-Trap? samplers and groundwater samples collected from monitoring wells verified the abundance of bacteria and enzymes capable of aerobically degrading TCE and 1,4-dioxane. Furthermore, phospholipid fatty acid analysis with stable isotope probes (PLFA-SIP) of the microbial community validated the ability for microbial degradation of TCE and 1,4-dioxane. Compound specific isotope analysis (CSIA) of groundwater samples for TCE resulted in δ(13)C values that indicated likely biodegradation of TCE in three of the four monitoring wells sampled. Results of the MNA evaluation showed that enzymes capable of aerobically degrading TCE and 1,4-dioxane were present, abundant, and active in the aquifer. Taken together, these results provide direct evidence of the occurrence of TCE and 1,4-dioxane biodegradation at the study site, supporting the selection of MNA as part of the final remedy at some point in the future.     

Estimating the aquatic emissions and fate of perfluorooctane sulfonate (PFOS) into the river Rhine

The sources, distribution, levels and sinks of perfluorooctane sulfonate (PFOS) estimated to be released from areas of high population density, have been explored using the river Rhine as a case study. A comparison between modelled and measured data is presented, along with analysis of the importance of PFOS sorption in riverine systems. PFOS releases into the Rhine were estimated to be 325-690 kg/yr based on per capita emission rates of 27-57 μg day(-1) from a population of 33 million living within a 50 km zone either side of the river. Sorption of PFOS to suspended particles and sediments may alter its fate in the aquatic environment. Therefore available measured and modelled partitioning data was assessed, and K(d) values (sorption coefficient) of 7.5 and 20 were selected. This resulted in sediment-water ratios of 23-76 : 1, which are similar to ratios reported in the literature, and resulted in modelled estimates that <20% of the total PFOS entering the Rhine binds to sediments or suspended particles. The calculated discharge from the Rhine to the North Sea based on measured data was 420-2200 kg/yr; our model predictions are in good agreement with these estimates. Emission trends were accurately predicted, suggesting population density can be effectively used as a surrogate for diffuse PFOS emissions from product use, while predicted concentrations were a factor of 2-4 below measured data showing the importance of other sources. Transfer of PFOS to sediment is estimated to be minimal, and consequently discharges to the North Sea are roughly equal to PFOS releases to river water.     

Mobile monitoring along a street canyon and stationary forest air monitoring of formaldehyde by means of a micro-gas analysis system

A micro-gas analysis system (μGAS) was developed for mobile monitoring and continuous measurements of atmospheric HCHO. HCHO gas was trapped into an absorbing/reaction solution continuously using a microchannel scrubber in which the microchannels were patterned in a honeycomb structure to form a wide absorbing area with a thin absorbing solution layer. Fluorescence was monitored after reaction of the collected HCHO with 2,4-pentanedione (PD) in the presence of acetic acid/ammonium acetate. The system was portable, battery-driven, highly sensitive (limit of detection = 0.01 ppbv) and had good time resolution (response time 50 s). The results revealed that the PD chemistry was subject to interference from O(3). The mechanism of this interference was investigated and the problem was addressed by incorporating a wet denuder. Mobile monitoring was performed along traffic roads, and elevated HCHO levels in a street canyon were evident upon mapping of the obtained data. The system was also applied to stationary monitoring in a forest in which HCHO formed naturally via reaction of biogenic compounds with oxidants. Concentrations of a few ppbv-HCHO and several-tens of ppbv of O(3) were then simultaneously monitored with the μGAS in forest air monitoring campaigns. The obtained 1 h average data were compared with those obtained by 1 h impinger collection and offsite GC-MS analysis after derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA). From the obtained data in the forest, daily variations of chemical HCHO production and loss are discussed.     

Long-term seasonal changes of the Danube River eco-chemical status in the region of Serbia

Seasonal spatial and temporal changes of selected eco-chemical parameters in section of the Danube River flowing through Serbia were analyzed. Data for electrical conductivity (EC), dry and suspended matter, residue on ignition, chemical oxygen demand (COD), biochemical oxygen demand (BOD-5), ultraviolet extinction, dissolved oxygen (DO), oxygen saturation, pH, nitrates, total phosphorus, and nitrogen were collected between 1992 and 2006. The use of monthly medians combined with linear regression and two-sided t test has been proven to be the best approach for resolving trends from natural variability of investigated parameters and for determining trend significance. Patterns of temporal changes between different months were examined. It was also determined that spatial trends of some parameters oscillate in predictable manner, increasing in one part of the year and declining in the other. Regression slope coefficients, an excellent indicator for determining when the water quality is changing the most along the course of the Danube, reach their maximum during summer for temperature (t), electric conductivity, nitrates, and total N, while in the same season suspended matter, COD, BOD-5, DO, and oxygen saturation coefficients reach their minimum. Correlations for used data sets of selected parameters were analyzed for better understanding of their behavior and mutual relations. It was observed that as Danube flows through Serbia, its general eco-chemical status either stagnates or improves, but the rate of river self-purification often depends on the season of the year.     

Chemical dynamics of the Sava riverine system

Presented here is a study of the geochemical dynamics of the entire River Sava watershed, a major tributary of the River Danube which has not previously been investigated. The sampling was performed at 33 selected locations along the main channel of the stream and at its largest tributaries during three sampling seasons (fall 2005, spring 2006 and fall 2006), going from headwater locations to the mouth near the confluence with the Danube. Almost 80% of the solutes are derived from carbonate mineral weathering and represent over 50% of specific HCO(3)(-) flux normalized to unit basin area at the mouth of the Danube. Statistical analysis indicates that agricultural and industrial sources contribute significantly to increased Na(+), K(+), Cl(-), SO(4)(2-) and NO(3)(-) concentrations in tributary waters. Different processes control the water chemistry along the course of the Sava's drainage-the upper reaches are largely regulated by contributions from carbonate mineral weathering, the middle reaches are influenced by agricultural activity and biological processes related to eutrophication, while the lower reaches tend to have more pronounced parameters related to the industrial processing along with leakages from municipal sanitary systems of these higher population density areas.