Light-induced heterogeneous ozone processing on organic coated particles: Kinetics and condensed-phase products

For the first time we investigated the effect of solar irradiation upon the heterogeneous ozonation of adsorbed 3,4,5-trimethoxybenzaldehyde on solid surface. Light-induced heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde adsorbed on silica particles were performed and the consecutive reaction products were identified. At an ozone mixing ratio of 250 ppb, the loss of 3,4,5-trimethoxybenzaldehyde ranged from 1.0 · 10^?6 s^?1 in the dark to 2.9 · 10^?5 s^?1 under light irradiation. Such large enhancement of 29 times clearly shows the importance of light (λ > 300 nm) during the heterogeneous ozonolysis on organic coated particles.The reaction products identified in this study (3,4,5-trimethoxybenzoic acid, syringic acid, methyl 3,4,5-trimethoxybenzoate) absorb light in the spectral window (λ > 300 nm) which implies that light-induced heterogeneous ozone processing can have an influence on the aerosol surfaces by changing their physico-chemical properties.The main identified product of the heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde under dark conditions and in presence of light was 3,4,5-trimethoxybenzoic acid. For this reason we estimated the carbon yield of 3,4,5-trimethoxybenzoic acid. Carbon yields of 3,4,5-trimethoxybenzoic acid decreased with increasing ozone mixing ratio; from 40% at 250 ppb to 15% at ≥2.5 ppm under dark conditions. At ozone mixing ratio (250 ppb–1 ppm), carbon yields of 3,4,5-trimethoxybenzaldehyde are relatively higher in the experiment under dark condition than under simulated solar light.     

Industrial ecology: a review

Industrial ecology is both a vision, a research field, and a source of inspiration for practical work. Its proponents aim to contribute to sustainable development by closing materials cycles and realising a fundamental paradigm shift in the thinking concerning industry–ecology relations. Dominant research lines in industrial ecology focus on industrial metabolism and life cycle tools. The underlying assumption is that the flow and transformation of materials can be managed through the correcting of market and regulatory failures which are causes of environmental degradation. This literature review suggests, on the one hand, that the manageability of the flow of materials is currently limited by market and regulatory failures which inhibit the implementation of the principles of industrial ecology and, on the other hand, that the flow and transformation of materials are only partly affected by prices, information and laws. Received: 9 September 1999 · Revised: 22 November 1999 · Accepted: 2 December 1999     

Trend analysis of urban NO2 concentrations and the importance of direct NO2 emissions versus ozone/NOx equilibrium

The annual air quality standard of NO₂ is often exceeded in urban areas near heavy traffic locations. Despite significant decrease of NO_x emissions in 1986–2005 in the industrial and harbour area near Rotterdam, NO₂ concentrations at the urban background remain at the same level since the end of the nineties. Trend analysis of monitoring data revealed that the ozone/NO_x equilibrium is a more important factor than increasing direct NO₂ emissions by traffic. The latter has recently been identified as an additional NO₂ source due to the introduction of oxy-catalytic converters in diesel vehicles and the growing number of diesel vehicles. However, in Rotterdam over the period 1986–2005 direct NO₂ emissions by road traffic only increased 3–4%. Due to the importance of the ozone/NO_x equilibrium, it is concluded that local NO_x emissions in Rotterdam need substantial reduction to achieve lower NO₂ urban background levels. This is a relatively costly abatement strategy and, therefore, a “hotspot” approach aiming at reducing NO_x emissions by local traffic measures is more effective to meet European air quality standards.     

Kinetic study of heterogeneous ozonolysis of alachlor, trifluralin and terbuthylazine adsorbed on silica particles under atmospheric conditions

To better understand the atmospheric behaviour of pesticides, heterogeneous ozonolysis of three herbicides (alachlor, terbuthylazine and trifluralin) adsorbed on silica particles were performed in a flow reactor. The experimental setup used in this study and previously validated (Pflieger et al., 2009) has been specially developed to investigate extremely slow reactivity. The pesticides were adsorbed on particles using a gas/solid adsorption equilibrium, in order to simulate atmospheric conditions. After exposure to ozone concentrations ranging from 5 to 41 ppm during 90 min to 6 h, the kinetics were calculated by comparing the initial and the remaining amounts of pesticides adsorbed on silica particles. This work offers the first results of heterogeneous ozonolysis of alachlor and trifluralin adsorbed on mineral particles. Although alachlor and terbuthylazine were expected to react with ozone, no degradation was observed which leads to a lifetime higher than 8 months towards ozonolysis (for 40 ppb of O₃). A significant degradation of trifluralin adsorbed on silica particles by heterogeneous ozonolysis was observed. The experimental data could be fit by both the Langmuir–Rideal and the Langmuir–Hinshelwood models resulting in atmospheric lifetimes (towards heterogeneous ozonolysis) of 40 and 32 days respectively (for 40 ppb of O₃). These results are discussed and compared to other studies.     

Maternal transfer of organochlorines and brominated flame retardants in blue tits (Cyanistes caeruleus)

Although eggs have frequently been used as a biomonitoring tool for contamination with organohalogenated pollutants (OHPs), few studies have investigated the processes of maternal transfer in birds. Here, maternal transfer of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated through comparison of the concentrations and profiles between whole homogenised female blue tits (Cyanistes caeruleus) and their eggs. In addition, we examined if there was an effect of laying order on the concentrations of PCBs, OCPs and PBDEs. PCBs were the most abundant contaminants in female blue tits and their eggs, followed by OCPs and PBDEs. Among the OCPs, p,p'-DDE was the most dominant compound and accounted for more than 80% of the sum OCPs. Egg concentrations decreased significantly in relation to the laying order from 1623+/-148 ng/g lipid weight (lw) to 1040+/-47 ng/g lw for the sum PCBs, from 342+/-24 ng/g lw to 235+/-17 ng/g lw for the sum OCPs and from 49+/-5 ng/g lw to 27+/-5 ng/g lw for the sum PBDEs. When reviewing all studies investigating laying order effects of OHPs in birds, no clear patterns emerged, which may be due to differences in study species and methodology among studies. Despite the fact that there were laying order effects in blue tit clutches, the variance in concentrations of PCBs and PBDEs was larger among clutches than within clutches. Variance in OCP concentrations among clutches was similar to the variance within clutches. These results suggest that one randomly collected blue tit egg from a clutch is useful as biomonitoring tool for PCBs and PBDEs, while for OCPs it is recommended to consistently use the same egg from the laying sequence as a biomonitoring tool. Lipid-normalized concentrations of sum PCBs, sum OCPs and sum PBDEs in female blue tits after clutch completion were comparable to the concentrations in the first-laid eggs. The egg/female lipid concentration ratios for sum PCBs, sum OCPs and sum PBDEs decreased significantly from 1.0+/-0.09 to 0.7+/-0.003, 1.1+/-0.1 to 0.7+/-0.02 and 1.2+/-0.14 to 0.8+/-0.05, respectively, during the course of egg laying. The profiles of the females and eggs differed significantly for the PCBs, OCPs and PBDEs. There was a higher contribution of lower chlorinated PCB congeners (CB 28, CB 52, CB 95, CB 101 and CB 110), BDE 183, p,p'-DDT and other less persistent OCPs in the females compared to their eggs. Maternal transfer in blue tits seemed to be selective for the more bioaccumulative and persistent congeners/compounds.     

Factors impacting on pharmaceutical leaching following sewage application to land

Sewage effluent application to land is a treatment technology that requires appropriate consideration of various design factors. Soil type, level of sewage pre-treatment and irrigation rate were assessed for their influence on the success of soil treatment in removing pharmaceuticals remaining after conventional sewage treatment. A large scale experimental site was built to assess treatment performance in a realistic environment. Of the factors investigated, soil type had the biggest impact on treatment performance. In particular, carbamazepine was very efficiently removed (>99%) when irrigated onto a volcanic sandy loam soil. This was in contrast to irrigation onto a sandy soil where no carbamazepine removal occurred after irrigation. Differences were likely caused by the presence of allophane in the volcanic soil which is able to accumulate a high level of organic matter. Carbamazepine apparent adsorption distribution coefficients (K(d)) for both soils when irrigated with treated sewage effluent were determined as 25 L kg(-1) for the volcanic soil and 0.08 L kg(-1) for the sandy soil. Overall, a volcanic soil was reasonably efficient in removing carbamazepine while soil type was not a major factor for caffeine removal. Removal of caffeine, however, was more efficient when a partially treated rather than fully treated effluent was applied. Based on the investigated pharmaceuticals and given an appropriate design, effluent irrigation onto land, in conjunction with conventional sewage treatment may be considered a beneficial treatment for pharmaceutical removal.     

Effects of a herbicide-insecticide mixture in freshwater microcosms: risk assessment and ecological effect chain

Effects of chronic application of a mixture of the herbicide atrazine and the insecticide lindane were studied in indoor freshwater plankton-dominated microcosms. The macroinvertebrate community was seriously affected at all but the lowest treatment levels, the zooplankton community at the three highest treatment levels, with crustaceans, caddisflies and dipterans being the most sensitive groups. Increased abundance of the phytoplankton taxa Cyclotella sp. was found at the highest treatment level. Threshold levels for lindane, both at population and community level, corresponded well with those reported in the literature. Atrazine produced fewer effects than expected, probably due to decreased grazer stress on the algae as a result of the lindane application. The safety factors set by the Uniform Principles for individual compounds were also found to ensure protection against chronic exposure to a mixture of a herbicide and insecticide at community level, though not always at the population level.     

An exposure study with polybrominated diphenyl ethers (PBDEs) in female European starlings (Sturnus vulgaris): toxicokinetics and reproductive effects

We exposed female European starlings to a pentabromodiphenyl ether (Penta-BDE) mixture through subcutaneous implants, and examined levels and profiles of polybrominated diphenyl ethers (PBDEs) together with reproductive effects. Sum PBDE levels increased significantly in the serum of the exposed females from 218 ± 43 to 23,400 ± 2035 pg/ml. Sum PBDE concentrations in the eggs of the exposed group ranged from 130 ± 12 to 220 ± 37 ng/g wet weight (ww). The profile in serum after egg laying was very similar to that in eggs. There were no detectable levels of HO-PBDEs in both serum and eggs. Fewer females of the exposed group initiated egg laying compared to the control group, although the difference was not significant. In addition, egg weight and volume were significantly higher in the exposed group. These results suggest that, at the investigated exposure levels (150 μg sum PBDEs/bird), PBDEs may have a negative effect on reproductive performance.     

Analytical developments and preliminary assessment of human exposure to organophosphate flame retardants from indoor dust

A new and efficient analytical method was developed and validated for the analysis of organophosphorus flame retardants (OPFRs) in indoor dust samples. This method involves an extraction step by ultrasonication and vortex, followed by extract clean-up with Florisil solid-phase extraction cartridges and analysis of the purified extracts by gas chromatography-mass spectrometry (GC-MS). Method recoveries ranged between 76 and 127%, except for volatile OPFRs, such as triethyl phosphate (TEP) and tri-(n-propyl) phosphate (TnPP), which were partially lost during evaporation steps. The between day precision on spiked dust samples was <14% for individual OPFRs, except for TEP, tri-iso-butyl phosphate (TiBP) and tri (2-butoxyethyl) phosphate (TBEP). Method limit of quantifications (LOQ) ranged between 0.02 μg/g (TnPP and tris(1-chloro-2-propyl phosphate (TCPP)) and 0.50 μg/g (TiBP). The method was further applied for the analysis of indoor dust samples taken from Flemish homes and stores. TiBP, TBEP and TCPP were most abundant OPFR with median concentrations of 2.99, 2.03 and 1.38 μg/g in house dust and of 1.04, 3.61, and 2.94 μg/g in store dust, respectively. The concentration of all OPFRs was at least 20 to 30 times higher compared to polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). Estimated exposure to OPFRs from dust ingestion ranged for individual OPFRs between <1 and 50 ng/kg body weight for adults and toddlers, respectively. The estimated body burdens were 1000 to 100 times below reference dose (RfD) values, except for the scenario with high dust ingestion and high concentrations of TBEP in toddlers, where intake was only 5 times below RfD. Exposure of non-working and working adults to OPFRs appeared to be similar, but in specific work environments, exposure to some OPFRs (e.g. TDCPP) was increased by a factor >5.