Desorption of PCDD/PCDF from municipal solid waste incinerator flyash under post-combustion plant conditions

The influence of temperature on the levels of PCDD and PCDF remaining in, and desorbed from, a municipal solid waste incinerator flyash was investigated by heating the ash to between 200 and 400 degrees C under a simulated flue gas for four days reaction time. Considerable desorption of PCDD/PCDF from the flyash was seen at 275 degrees C and above. Maximum desorption occurred at 350 degrees C, with the equivalent of nearly eight times the total PCDD/PCDF concentration of the original flyash being lost to the vapour phase per unit mass of initial flyash. The I-TEQ value of the desorbed PCDD/PCDF was considerable, being over fourteen times that of the original flyash at 325 degrees C. The results indicate that formation of PCDD/PCDF on flyash deposits in the post-combustion plant of incinerators can result in the release of significant amounts of PCDD/PCDF to the flue gas stream.     

PCDD/PCDF Isomer patterns in waste incinerator flyash and desorbed into the gas phase in relation to temperature

The influence of temperature on the PCDD and PCDF isomer profiles of a municipal waste incinerator flyash and the PCDD/PCDF desorbed from the ash under an inert atmosphere was investigated using a bench-scale reactor. Exposure to temperatures of 250 degrees C and above resulted in significant changes in the distribution of isomers within most dioxin and furan congener groups. The PCDD content tended to become more evenly distributed across the range of isomers than was the case for the raw flyash, while the PCDF content became concentrated across a relatively lower number of isomers. In most cases the desorbed PCDD/PCDF were mainly mono- to tri-chlorinated, and hence had a relatively low I-TEQ value. The isomer profiles of the desorbed species were also influenced by temperature. There were some significant differences between the PCDF isomer profiles of the desorbed species and those of the treated flyashes under the same conditions, but no clear differences between the PCDD isomer profiles.     

Testing and Improving Temperature Thresholds for Snow and Rain Prediction in the Western United States

The phase of precipitation at the land surface is critical to determine the timing and amount of water available for hydrological and ecological systems. However, there are few techniques to directly observe the precipitation phase and many prediction tools apply a single temperature threshold (e.g., 0°C) to determine phase. In this paper, we asked two questions: (1) what is the accuracy of default and station optimized daily temperature thresholds for predicting precipitation phase and (2) what are the regions and conditions in which typical temperature‐based precipitation phase predictions are most suited. We developed a ground truth dataset of rain vs. snow using an expert decision‐making system based on precipitation, snow depth, and snow water equivalent observations. This dataset was used to evaluate the accuracy of three temperature‐threshold‐based techniques of phase classification. Optimizing the temperature threshold improved the prediction of precipitation phase by 34% compared to using 0°C threshold. Developing a temperature threshold based on station elevation improved the error by 12% compared with using the 0°C temperature threshold. We also found the probability of snow as a function of temperature differed among ecoregions, which suggests a varied response to future climate change. These results highlight a current weakness in our ability to predict the effects of regional warming that could have uneven impacts on water and ecological resources.     

Influence of suspended particles on the emission of organophosphate flame retardant from insulation boards

The influence of the presence of the so-called seed particles on the emission rate of Tris (1-chloroisopropyl) phosphate (TCIPP) from polyisocyanurate (PIR) insulation boards was investigated in this study. Two Field and Laboratory Emission Test cells (FLEC) were placed on the surface of the same PIR board and respectively supplied with clean air (reference FLEC) and air containing laboratory-generated soot particles (test FLEC). The behavior of the area-specific emission rates (SER _A ) over a time period of 10 days was studied by measuring the total (gas?+?particles) concentrations of TCIPP at the exhaust of each FLEC. The estimated SER _A of TCIPP from the PIR board at the quasi-static equilibrium were found to be 0.82 μg m^?2 h^?1 in the absence of seed particles, while the addition of soot particles led to SER _A of 2.16 μg m^?2 h^?1. This indicates an increase of the SER _A of TCIPP from the PIR board with a factor of 3 in the presence of soot particles. The TCIPP partition coefficient to soot particles at the quasi-static equilibrium was 0.022?±?0.012 m³ μg^?1. In the next step, the influence of real-life particles on TCIPP emission rates was investigated by supplying the test FLEC with air from a professional kitchen where mainly frying and baking activities took place. Similar to the reference FLEC outcomes, SER _A was also found to increase in this real-life experiment over a time period of 20 days by a factor 3 in the presence of particles generated during cooking activities. The median value of estimated particle–gas coefficient for this test was 0.062?±?0.037 m³ μg^?1.

     

Farm, land, and soil nitrogen budgets for agriculture in Europe calculated with CAPRI

We calculated farm, land, and soil N-budgets for countries in Europe and the EU27 as a whole using the agro-economic model CAPRI. For EU27, N-surplus is 55 kg N ha⁻¹ yr⁻¹ in a soil budget and 65 kg N₂O–N ha⁻¹ yr⁻¹ and 67 kg N ha⁻¹ yr⁻¹ in land and farm budgets, respectively. NUE is 31% for the farm budget, 60% for the land budget and 63% for the soil budget. NS values are mainly related to the excretion (farm budget) and application (soil and land budget) of manure per hectare of total agricultural land. On the other hand, NUE is best explained by the specialization of the agricultural system toward animal production (farm NUE) or the share of imported feedstuff (soil NUE). Total N input, intensive farming, and the specialization to animal production are found to be the main drivers for a high NS and low NUE.     

Does Including Soil Moisture Observations Improve Operational Streamflow Forecasts in Snow‐Dominated Watersheds?

Changing climate and growing water demand are increasing the need for robust streamflow forecasts. Historically, operational streamflow forecasts made by the Natural Resources Conservation Service have relied on precipitation and snow water equivalent observations from Snow Telemetry (SNOTEL) sites. We investigate whether also including SNOTEL soil moisture observations improve April‐July streamflow volume forecast accuracy at 0, 1, 2, and 3‐month lead times at 12 watersheds in Utah and California. We found statistically significant improvement in 0 and 3‐month lead time accuracy in 8 of 12 watersheds and 10 of 12 watersheds for 1 and 2‐month lead times. Surprisingly, these improvements were insensitive to soil moisture metrics derived from soil physical properties. Forecasts were made with volumetric water content (VWC) averaged from October 1 to the forecast date. By including VWC at the 0‐month lead time the forecasts explained 7.3% more variability and increased the streamflow volume accuracy by 8.4% on average compared to standard forecasts that already explained an average 77% of the variability. At 1 to 3‐month lead times, the inclusion of soil moisture explained 12.3‐26.3% more variability than the standard forecast on average. Our findings indicate including soil moisture observations increased statistical streamflow forecast accuracy and thus, could potentially improve water supply reliability in regions affected by changing snowpacks.     

Biomagnification of anthropogenic and naturally-produced organobrominated compounds in a marine food web from Sydney Harbour, Australia

Polybrominated diphenyl ethers (PBDEs) and naturally-produced organobrominated compounds, such as methoxylated PBDEs (MeO-PBDEs), have been scarcely studied in the Southern Hemisphere. Yet, sources of the latter group of compounds were found in Southern regions, specifically in Australia. The environmental distribution and biomagnification potential of organobrominated compounds were therefore investigated in a representative aquatic food chain (invertebrates and fish) from the Sydney Harbour, Australia. Mean PBDE concentrations ranged from 6.4 ng/g lipid weight (lw) in squid to 115 ng/g lw in flounder. BDE 47 was the dominant congener, followed by BDE 100. Mean levels of MeO-PBDEs (sum of congeners 2’-MeO-BDE 68 and 6-MeO-BDE 47) were as high as 110 ng/g lw in tailor, with a slight dominance of 2’-MeO-BDE 68. Polybrominated hexahydroxanthene derivates (PBHDs), another class of naturally-produced compounds, were found at variable concentrations and ranged from 4.7 ng/g lw in fanbelly and 146 ng/g lw in tailor. The tribrominated PBHD isomer dominated in the samples, except for luderick and squid. The lower levels of PBDEs found in luderick from the harbour compared to those obtained from the upper Parramatta River indicated a terrestrial (anthropogenic) origin of PBDEs, while the higher levels of MeO-PBDEs and PBHDs in the samples from the harbour confirmed the marine (natural) origin of these compounds. The highest trophic magnification factor (TMF) was found for sum PBDEs (3.9), while TMFs for sum MeO-PBDEs and sum PBHDs were 2.9 and 3.4, respectively. This suggests that biomagnification occurs in the studied aquatic food chain for anthropogenic brominated compounds, but also for the naturally-produced organobromines.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Organochlorine and heavy metals in newborns: Results from the Flemish Environment and Health Survey (FLEHS 2002–2006)

To collect regional information on internal levels of pollutants in humans in Flanders, 1196 mother–child pairs were systematically recruited in 2002–2003 via 25 maternities across Flanders. Cd, Pb, PCB congeners 118, 170, 138, 153 and 180, p,p′-DDE — a key metabolite of DDT- and hexachlorobenzene (HCB) were measured in cord blood or plasma. Cd was detected in 64% of the samples (geometric mean 0.21 µg/L cord blood). p,p′-DDE (110 ng/g plasma lipids) and Pb (14.7 µg/L blood), were measurable in nearly all samples. The individual PCB congeners could be detected in 40 to 81% of the newborns (138 + 153 + 180 = 64.4 ng/g plasma lipids). HCB (18.9 ng/g plasma lipids) and dioxin-like compounds measured by DR-CALUX® (23 pg CALUX-TEQ/g lipids) were above detection limit in more than 75% of the samples. Age and smoking habits of the mothers, did not influence the cord blood Pb and Cd levels. The organochlorines increased 4 to 9% per year of the mother's age (partial R² = 0.05 to 0.22). Mothers had 2.6% less PCBs in cord blood (partial R² = 0.02) for each unit increase in pre-pregnancy BMI. Season of delivery, breastfeeding previous children or consumption of local dairy products, were minor determinants. Up to 20% of the variability in organochlorine concentrations was explained by residence area. It was concluded that the place of birth in Flanders is an important determinant of the load of pollutants measured at the start of life. This underlines the validity of human biomonitoring on (relatively) small geographical scale.     

Biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in harbour seals and harbour porpoises from the Southern North Sea

Harbour seals and harbour porpoises are top predator species from the North Sea, have long life spans and hence, are known to accumulate high levels of anthropogenic contaminants. To gain knowledge about the behaviour of naturally-produced compounds in these marine mammals, the biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was assessed. The biomagnification of MeO-PBDEs (2′-MeO-BDE 68 and 6-MeO-BDE 47) was lower in harbour seals (all biomagnification factors (BMFs) < 1) compared to the same age–gender groups of the harbour porpoises (all BMFs > 1). This may indicate a better metabolic breakdown of MeO-PBDEs in harbour seals, as was previously suggested for polybrominated diphenyl ethers (PBDEs). In both predators, 6-MeO-BDE 47 had the highest concentrations (range: 45–483 ng/g lw and 2–38 ng/g lw for harbour porpoises and seals, respectively) compared to 2′-MeO-BDE 68 (range: 2–28 ng/g lw and 1–6 ng/g lw for harbour porpoises and seals, respectively). In general, the highest concentrations were found in juveniles, suggesting an increased biotransformation capacity with age or the influence of dilution by growth for both species. Here we show that naturally-produced brominated organic compounds can biomagnify and accumulate in North Sea top predators, although to a lesser extent than anthropogenic lipophilic contaminants, such as polychlorinated biphenyls (PCBs) or PBDEs.