Polychlorinated biphenyls (PCBs) in air and seawater of the Atlantic Ocean: sources, trends and processes

Air and seawater samples were collected on board the RV Polarstern during a cruise from Bremerhaven, Germany to Cape Town, South Africa from October-November 2005. Broad latitudinal trends were observed with the lowest sigma27PCB air concentration (approximately 10 pg m(-3)) in the South Atlantic and the highest (approximately 1000 pg m(-3)) off the west coast of Africa. Sigma(ICES)PCBs ranged from 3.7 to 220 pg m(-3) in air samples and from 0.071 to 1.7 pg L(-1) in the dissolved phase seawater samples. Comparison with other data from cruises in the Atlantic Ocean since 1990 indicate little change in air concentrations over the remote open ocean. The relationship of gas-phase partial pressure with temperature was examined using the Clausius-Clapeyron equation; significant temperature dependencies were found for all PCBs over the South Atlantic, indicative of close air-water coupling. There was no temperature dependence for atmospheric PCBs overthe North Atlantic, where concentrations were controlled by advection of contaminated air masses. Due to large uncertainties in the Henry's Law Constant (HLC), fugacity fractions and air-water exchange fluxes were estimated using different HLCs reported in the literature. These suggest that conditions are close to air-water equilibrium for most of the ocean, but net deposition is dominating over volatilization in parts of the transect. Generally, the tri- and tetrachlorinated homologues dominated the total flux (> 70%). Total PCB fluxes (28, 52, 118, 138, and 153) ranged from -7 to 0.02 ng m(-2) day(-1).     

Organic carbon in Antarctic snow: spatial trends and possible sources

Organic carbon records in Antarctic snow are sparse despite the fact that it is of great significance to global carbon dynamics, snow photochemistry, and air-snow exchange processes. Here, surface snow total organic carbon (TOC) along with sea-salt Na(+), dust, and microbial load of two geographically distinct traverses in East Antarctica are presented, viz. Princess Elizabeth Land (PEL, coast to 180 km inland, Indian Ocean sector) and Dronning Maud Land (DML, ～110-300 km inland, Atlantic Ocean sector). TOC ranged from 88 ± 4 to 928 ± 21 μg L(-1) in PEL and 13 ± 1 to 345 ± 6 μg L(-1) in DML. TOC exhibited considerable spatial variation with significantly higher values in the coastal samples (p < 0.001), but regional variation was insignificant within the two transects beyond 100 km (p > 0.1). Both distance from the sea and elevation influenced TOC concentrations. TOC also showed a strong positive correlation with sea-salt Na(+) (p < 0.001). In addition to marine contribution, in situ microorganisms accounted for 365 and 320 ng carbon L(-1) in PEL and DML, respectively. Correlation with dust suggests that crustal contribution of organic carbon was marginal. Though TOC was predominantly influenced by marine sources associated with sea-spray aerosols, local microbial contributions were significant in distant locations having minimal sea-spray input.     

Transformation processes,pathways, and possible sources of distinctive polychlorinated dibenzo-p-dioxin signatures in sink environments

In recent years, studies on environmental samples with unusual dibenzo-p-dioxin (PCDD) congener profiles were reported from a range of countries. These profiles, characterized by a dominance of octachlorinated dibenzodioxin (OCDD) and relatively low in dibenzofuran (PCDF) concentrations, could not be attributed to known sources or formation processes. In the present study, the processes that result in these unusual profiles were assessed using the concentrations and isomer signatures of PCDDs from dated estuarine sediment cores in Queensland, Australia. Increases in relative concentrations of lower chlorinated PCDDs and a relative decrease of OCDD were correlated with time of sediment deposition. Preferred lateral, anaerobic dechlorination of OCDD represents a likely pathway for these changes. In Queensland sediments, these transformations result in a distinct dominance of isomers fully chlorinated in the 1,4,6,9-positions (1,4-patterns), and similar 1,4-patterns were observed in sediments from elsewhere. Consequently, these environmental samples may not reflect the signatures of the original source, and a reevaluation of source inputs was undertaken. Natural formation of PCDDs, which has previously been suggested, is discussed; however, based on the present results and literature comparisons, we propose an alternative scenario. This scenario hypothesizes that an anthropogenic PCDD precursor input (e.g. pentachlorophenol) results in the contamination. These results and hypothesis imply further investigations are warranted into possible anthropogenic sources in areas where natural PCDD formation has been suggested.     

Using passive air samplers to assess urban-rural trends for persistent organic pollutants and polycyclic aromatic hydrocarbons. 2. Seasonal trends for PAHs, PCBs, and organochlorine pesticides

This is the second of two papers demonstrating the feasibility of using passive air samplers to investigate persistent organic pollutants along an urban-rural transect in Toronto. The first paper investigated spatial trends for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). This second paper investigates the seasonality of air concentrations for polycyclic aromatic hydrocarbons (PAHs), PCBs, and OCPs along this transect. Air samplers, consisting of polyurethane foam (PUF) disks housed in stainless steel domed chambers, were deployed for three 4-month integration periods from June 2000 to July 2001. The seasonal variations of derived air concentrations for PAHs, PCBs, and OCPs reflected the different source characteristics for these compounds. PAHs showed a strong urban-rural gradient with maximum concentrations at urban sites during the summer period (July-October). These high summer values in Toronto were attributed to increases in evaporative emissions from petroleum products such as asphalt. PCBs also exhibited a strong urban-rural gradient with maximum air concentrations (approximately 2-3 times higher) during the spring period (April-June). This was attributed to increased surface-air exchange of PCBs that had accumulated in the surface layer over the winter. alpha-HCH was fairly uniformly distributed, spatially and temporally, as expected. This pattern and the derived air concentration of approximately 35 to approximately 100 pg m(-3) agreed well with high volume air data from this region, adding confidence to the operation of the passive samplers and showing that site-to-site differences in sampling rates was not an issue. For other OCPs, highest concentrations were observed during the spring period. This was associated with either (i) their local and/or regional application (gamma-HCH, endosulfan) and (ii) their revolatilization (chlordanes, DDT isomers, dieldrin, and toxaphene). Principal component analysis resulted in clusters for the different target chemicals according to their chemical class/source type. The results of this study demonstrate how such a simple sampling technique can provide both spatial and seasonal information. These data, integrated over seasons, can be used to evaluate contaminant trends and the potential role of large urban centers as sources of some semivolatile compounds to the regional environment, including the Great Lakes ecosystem.     

Atmospheric reactive nitrogen in china: sources, recent trends, and damage costs

Human activities have intensely altered the global nitrogen cycle and produced nitrogenous gases of environmental significance, especially in China where the most serious atmospheric nitrogen pollution worldwide exists. We present a comprehensive assessment of ammonia (NH(3)), nitrogen oxides (NO(x)), and nitrous oxide (N(2)O) emissions in China based on a full cycle analysis. Total reactive nitrogen (Nr) emission more than doubled over the past three decades, during which the trend of increase slowed for NH(3) emissions after 2000, while the trend of increase continued to accelerate for NO(x) and N(2)O emissions. Several hotspots were identified, and their Nr emissions were about 10 times higher than others. Agricultural sources take 95% of total NH(3) emission; fossil fuel combustion accounts for 96% of total NO(x) emission; agricultural (51%) and natural sources (forest and surface water, 39%) both contribute to the N(2)O emission in China. Total atmospheric Nr emissions related health damage in 2008 in China reached US$19-62 billion, accounting for 0.4-1.4% of China's gross domestic product, of which 52-60% were from NH(3) emission and 39-47% were from NO(x) emission. These findings provide policy makers an integrated view of Nr sources and health damage to address the significant challenges associated with the reduction of air pollution.     

Latitudinal fractionation of polychlorinated biphenyls in surface seawater along a 62 degrees N-89 degrees N transect from the southern Norwegian Sea to the North Pole area

Surface seawater concentrations of PCBs, relative congener abundance, and possible effects of cold condensation were studied along a transect from the southern Norwegian Sea to the central Arctic Ocean (62 degrees N-89 degrees N). Large volume samples were collected from an ice breaker using a stainless steel surface seawater intake connected online to an ultra-clean laboratory. Concentrations of all studied PCB congeners, except for trichlorinated PCB 18, decreased with latitude. For instance, PCB 52 decreased from 470 fg L(-1) at 62 degrees N to 110 fg L(-1) at 89 degrees N and PCB 180 from 110 to 12 fg L(-1). Concentrations in the central Arctic Ocean were on the order of 10-100 fg L(-1) for the most abundant congeners. The relative contribution oftrichlorinated PCBs to the total PCB concentration increased with latitude, the tetrachlorinated contribution to the total PCBs did not show any correlation to latitude, and the relative contribution of heavier congeners decreased with latitude. This study establishes the occurrence at very low abundances of PCBs in seawater in the central Arctic Ocean and demonstrates a northward concentration decrease. The latitudinal shift in congener pattern is reflecting the relative propensity of the PCB congeners to undergo long-range transport in the Arctic and is consistent with their relative vapor pressures.     

Passive-sampler derived air concentrations of persistent organic pollutants on a north-south transect in Chile

Passive air samplers consisting of polyurethane foam (PUF) disks, were deployed in six locations in Chile along a north-south transect to investigate gas-phase concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs). The study provides new information on air concentrations of these persistent organic pollutants (POPs) which is lacking in this region. It also provides insight into potential sources and long-range transport (LRT). The samplers were deployed for a 2-month period in five remote sites and one site in the city of Concepción. Mean concentrations (pg m(-3)) for sigmaPCB were 4.7 +/- 2.7 at remote sites and 53 +/- 13 in Concepción. PCB levels at remote sites were related to proximity to urban source regions and/or air back trajectories. With the exception of endosulfan I, mean concentrations (pg m(-3)) of OCPs at background sites were consistently low: 5.4 +/- 1.4 for alpha-HCH, 7.0 +/- 1.1 for gamma-HCH, 2.5 +/- 0.5 for TC, 2.5 +/- 0.6 for CC, 1.9 +/- 1.2 for dieldrin, and less than 3.5 for toxaphene. Endosulfan I showed a decreasing concentration gradient from 99 to 3.5 pg m(-3) from the north to south of Chile. Concentrations of OCPs in the Concepción City were generally 10-20 times higher than at the background sites suggesting continued usage and/or re-emission from past use. For instance, at remote sites, the alpha/gamma ratio (0.76) was typical of background air, while the ratio in Concepción (0.12) was consistent with fresh use of gamma-HCH. Levels of sigmaPBDEs were below the detection limit of 6 pg m(-3) at all sites.     

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.     

Concentrations of polybrominated diphenyl ethers in air and soil on a rural-urban transect across a major UK conurbation

Polybrominated diphenyl ethers (PBDEs) were measured in air (using PUF disk passive samplers) and soil samples taken at approximately monthly intervals over 1 year at 10 locations on a transect across the West Midlands of the UK. Concentrations in air are consistent with those detected elsewhere in Europe and the Great Lakes basin. Concentrations in soil fall within the range reported for rural woodland and grassland soils in the UK and Norway. In both air and soil, concentrations clearly decrease with increasing distance from the city center, supporting the existence of an urban "pulse", indicating the West Midlands conurbation to be a source of PBDEs to the wider environment. Examination of seasonal trends revealed no evidence of a "spring pulse" in concentrations in air, with no summer peak in concentrations in air observed for 70% of sites. The PBDE congener pattern in air differs from that in soil, with ratios of congeners 47:99 higher in air than in soil. It is hypothesized that PBDEs volatilize from treated products indoors, before ventilating outdoors, where congener 99 undergoes preferential atmospheric deposition and accumulation in soil.     

Atmospheric methane: trends and cycles of sources and sinks

For more than 20 years the global emissions and the lifetime of methane have probably been constant, so the buildup of methane in the atmosphere has been slowing down for as long. During this time, there have been periodic events occurring every seven to eight years, when global methane concentrations increased by some 10 ppb and later fell back, in some cases due to temporary increases of emissions from the northern tropics that spread to the global scale. These conclusions are derived from the accumulated global observations that now span 23 years and define the role of human activities in the recent cycle of atmospheric methane.     

Polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air of Hangzhou, China

Twelve polycyclic aromatic hydrocarbons were simultaneously measured in indoor and outdoor air of eight homes in Hangzhou, China in both summer and autumn in 1999. It was observed that the sum of PAHs concentrations in indoor air were ranged from 1.418 to 20.466 micrograms/m3 in summer and from 3.897 to 29.852 micrograms/m3 in autumn; the corresponding concentrations in outdoor air were between 1.380 and 20.468 micrograms/m3 in the summer and between 2.721 and 30.678 micrograms/m3 in autumn. The PAHs concentrations in indoor air generally exceeded that in the corresponding outdoor air. It was indicated that the two-, three-, and four-ring PAHs were predominantly in vapor phase, while the five-ring PAHs were primarily associated with the particulate phase. The fraction of PAHs in vapor phase will increase with the increase of temperature. Among the 12 PAHs, naphthalene was the most abundant PAHs found in indoor and outdoor air. Both in summer and autumn, it contributed more than 60% to the sum of PAHs. Because of the different functions and ventilation conditions, the concentrations of PAHs in the rooms were bedroom > kitchen > living room > balcony. By the contrast of BaP concentrations in smoker and nonsmoker's homes, we know that smoking in indoors could contribute 67% of BaP to the homes.     

Potential sources of pesticides,PCBs, and PAHs to the atmosphere of the Great Lakes

A probabilistic model called the potential source contribution function (PSCF) has been used to estimate atmospheric source regions of polycyclic aromatic hydrocarbons (PAHs), chlorinated pesticides, and polychlorinated biphenyls (PCBs) to the Great Lakes. This model allows us to map each compound's source region on a 0.5 degrees x 0.5 degrees latitude/longitude grid centered over the Great Lakes basin. PCBs primarily have urban sources, the strengths of which vary. Like PCBs, PAHs show a strong urban signature, but these compounds also seem to come from rural sites. The source regions of PAH become less distinct as the molecular weight of the compound increases. Since reactivity increases with PAH size, this diminishing trend may be an indication that atmospheric degradation plays a large role in PAH transport. The pesticides have the strongest source regions and are typically transported the farthest, often from areas distant from the Great Lakes basin.     

Changing trends in sulfur emissions in Asia: implications for acid deposition,air pollution,and climate

In the early 1990s, it was projected that annual SO2 emissions in Asia might grow to 80-110 Tg yr(-1) by 2020. Based on new high-resolution estimates from 1975 to 2000, we calculate that SO2 emissions in Asia might grow only to 40-45 Tg yr(-1) by 2020. The main reason for this lower estimate is a decline of SO2 emissions from 1995 to 2000 in China, which emits about two-thirds of Asian SO2. The decline was due to a reduction in industrial coal use, a slowdown of the Chinese economy, and the closure of small and inefficient plants, among other reasons. One effect of the reduction in SO2 emissions in China has been a reduction in acid deposition not only in China but also in Japan. Reductions should also improve visibility and reduce health problems. SO2 emission reductions may increase global warming, but this warming effect could be partially offset by reductions in the emissions of black carbon. How SO2 emissions in the region change in the coming decades will depend on many competing factors (economic growth, pollution control laws, etc.). However a continuation of current trends would result in sulfur emissions lower than any IPCC forecasts.     

Field validation of polyethylene passive air samplers for parent and alkylated PAHs in Alexandria, Egypt

Polyethylene samplers (PEs) were deployed at 11 locations in Alexandria, Egypt during summer and winter to test and characterize them as passive samplers for concentrations, sources, and seasonal variations of atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). PE-air equilibrium was attained faster for a wider range of PAHs during the winter season possibly due to increased wind speeds. Calculated PE-air partitioning constants, K(PE-A), in our study [Log K(PE-A) = 0.9426 × Log K(OA) - 0.022 (n = 12, R(2) = 0.99, Std error = 0.053)] agreed with literature values within <46%. For parent (except naphthalene), mono- and dialkylated PAHs, active sampling based concentrations of PAHs were within an average factor of 1.4 (1.0-5.6) compared to the PE based values. For C(3-4) alkylated PAHs, K(PE-A) values were lower than predicted, on average by ~0.8 log units per carbon in the alkylation. Enthalpies of vaporization (ΔH(vap)) accurately corrected K(PE-A)s for temperature differences between winter and summer sampling. PAH profiles were dominated by naphthalene, phenanthrene, and alkylated phenanthrenes. Calculated diagnostic ratios indicated that PAHs originated mainly from vehicle emissions.     

Evaluating sources of PAHs in urban streams based on land use and biomonitors

Toxic polycyclic aromatic hydrocarbons (PAHs) can be found in wastewaters and sewages released from industries and/or urban areas. When discharged untreated to stream waters, they can be a problem to human health. This work represents the first attempt to use PAH and metal concentrations in aquatic moss transplants together with land-use information to identify water pollution sources in urban areas. To do this, the moss Fontinalis antipyretica was collected from a natural stream and transplanted to four different streams in a densely populated area of Lisbon, Portugal. After three months of exposure, mosses were collected and analyzed for metals and for the 16 priority PAHs recommended by the U.S. EPA. Urban streams seem to have a scattered contamination of 6-ring PAHs. Correlations among land-use, metal concentrations, and PAH concentrations indicated that areas occupied by activities of tertiary and industrial sectors had higher PAH concentrations in transplanted mosses, mainly for the sum of the 16 EPA-PAHs and for the 2-, 3- and 5-ringed PAHs, than areas occupied by urban and wooded areas. These PAHs were associated with enhanced Zn and Cu and land use activities that linked the sites to high traffic density. Industrial land use influences PAH concentration in water up to 1000 m of distance from the stream, whereas tertiary sector land use influences it up to 500 m.     

Manufacturing origin of perfluorooctanoate (PFOA) in Atlantic and Canadian Arctic seawater

The extent to which different manufacturing sources and long-range transport pathways contribute to perfluorooctanoate (PFOA) in the world's oceans, particularly in remote locations, is widely debated. Here, the relative contribution of historic (i.e., electrochemically fluorinated) and contemporary (i.e., telomer) manufacturing sources was assessed for PFOA in various seawater samples by an established isomer profiling technique. The ratios of individual branched PFOA isomers were indistinguishable from those in authentic historic standards in 93% of the samples examined, indicating that marine processes had little influence on isomer profiles, and that isomer profiling is a valid source apportionment tool for seawater. Eastern Atlantic PFOA was largely (83-98%) of historic origin, but this decreased to only 33% close to the Eastern U.S. seaboard. Similarly, PFOA in the Norwegian Sea was near exclusively historic, but the relative contribution decreased to ～50% near the Baltic Sea. Such observations of contemporary PFOA in coastal source regions coincided with elevated concentrations, suggesting that the continued production and use of PFOA is currently adding to the marine burden of this contaminant. In the Arctic, a spatial trend was observed whereby PFOA in seawater originating from the Atlantic was predominantly historic (up to 99%), whereas water in the Archipelago (i.e., from the Pacific) was predominantly of contemporary origin (as little as 17% historic). These data help to explain reported temporal and spatial trends from Arctic wildlife biomonitoring, and suggest that the dominant PFOA source(s) to the Pacific and Canadian Arctic Archipelago are either (a) from direct emissions of contemporary PFOA via manufacturing or use in Asia, or (b) from atmospheric transport and oxidation of contemporary PFOA-precursors.     

Brominated flame retardants in seawater and atmosphere of the Atlantic and the Southern Ocean

Seawater and air samples were collected aboard the FS Polarstern during the cruises ANT-XXV/1 + 2 in the Atlantic and Southern Ocean in 2008. The particulate and dissolved phase in water and particulate and gaseous phase in air were analyzed separately for nine polybrominated diphenyl ethers (PBDEs) and six non-PBDE brominated flame retardants (BFRs). Air concentrations of 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and hexabromobenzene (HBB) in the gaseous and particulate phase (median = 0.56 pg m(-3) for DPTE and 0.92 pg m(-3) for HBB) were comparable to ∑(9)PBDEs (1.0 pg m(-3)). Pentabromotoluene (PBT) was detectable in ～30% of the gaseous phase samples, whereas concentration of 2,4,6-tribromophenyl allylether (ATE), hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) and 2-ethyl-1-hexyl 2,3,4,5-tetrabromobenzoate (EHTBB) were below their method detection limits. DPTE, and PBDEs were also found in seawater at low pg per liter levels. Elevated seawater concentrations of PBDEs and DPTE were measured in the English Channel and close to South African coast. Concentrations of DPTE, BDE-47, and BDE-99 in the atmosphere generally decreased from Europe toward the Southern Ocean, whereas no latitudinal trend was observed in seawater. Air-water exchange gradients suggested net deposition dominates for all selected substances. The medians of net deposition fluxes for the air-water gas exchange were 83, 21, 69, 20, and 781 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB, whereas medians of dry deposition fluxes were 2.0, 0.3, 1.2, 1.0, and 0.5 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB. Overall, these results highlight the important role of the long-range atmospheric transport of PBDE and non-PBDE BFRs to remote regions.     

Polycyclic aromatic hydrocarbons in urban air particulate matter: decadal and seasonal trends,chemical degradation,and sampling artifacts

Aerosol filter samples collected at a major urban traffic junction (LKP) and at a suburban residential location (IWC) in the metropolitan area of Munich (Germany) throughout the years 2001 and 2002 have been analyzed for 12 of the 16 EPA priority polycyclic aromatic hydrocarbon (PAH) pollutants by liquid chromatography with fluorescence detection. The mean mass concentration of the sum of all investigated PAH in the sampled air at LKP (1.9-5.0 ng m(-3)) was roughly two times higher than at IWC (0.8-2.9 ng m(-3)), and at both locations it was about 2-3 times higher in winter (heating season) than in summer and spring or autumn. Comparisons with earlier measurement campaigns indicate a steep decrease of PAH abundance by almost an order of magnitude from 1980 to 1993 and a much slower decrease since then. Distinctly different seasonal trends and short-term fluctuations have been observed for semivolatile 3- and 4-ring PAH and for particle-bound 5- and 6-ring PAH. Based on systematic correlation analyses with a wide range of air quality parameters, most of the differences can be attributed to not only varying emissions but also chemical reactions with atmospheric oxidants which were found to play an important role. The results of denuder experiments prove that substantial degradation of the particularly toxic tracer benzo[a]pyrene and of the other investigated 5- and 6-ring PAH can occur during filter sampling and on airborne particles (formation of oxygenated and nitrated derivatives). Filter reaction artifacts are shown to lead to an underestimation of the actual PAH content of urban air particulate matter by up to 100% of the measurement value or more, with a near-linear dependence on ozone volume mixing ratio. The role and applicability of ozone as a tracer of atmospheric oxidizing capacity for particle-bound PAH is discussed and confirmed by comparison with earlier investigations and by complementary laboratory experiments (reaction kinetics and product studies).     

Simultaneous assessment of sources, processes, and factors influencing herbicide losses to surface waters in a small agricultural catchment

To take appropriate measures to minimize agricultural herbicide inputs into surface waters, detailed knowledge is required about all the factors that control the losses of a given compound from point sources (i.e., farmyards) as well as from the diffuse sources (i.e., the fields) within a given catchment. In this and in a companion paper, we present the results of a comprehensive field study, in which the temporal and spatial variability of the losses of three herbicides (atrazine, dimethenamid, and metolachlor) into the surface waters within a small catchment (2.1 km2) were investigated on different scales (i.e., field scale to whole catchment) after a controlled application of the compounds. In this paper, we discuss the loss dynamics of the three herbicides (and some of their metabolites) from the whole catchment over a period of 67 d after application. An identical mixture of the three herbicides was applied on 13 cornfields within 12 h, allowing for a comparison of their losses under identical meteorological conditions. Thanks to a high temporal sampling resolution, it was possible to distinguish between losses from a farmyard and losses from the fields. Farmyard losses contributed less than 20% to the total loads but caused the highest concentrations. The major herbicide losses from the agricultural fields occurred during the first two rain events after application that led to significant surface runoff and preferential flow into tile drains. In the soils of all fields, dimethenamid declined somewhat faster than atrazine and metolachlor, whereas atrazine was mobilized most effectively to runoff water. Relative losses of the three compounds did not vary by more than a factor of 3 (0.82, 0.27, and 0.41% of the mass applied for atrazine, dimethenamid, and metolachlor, respectively). Highest peak concentrations at the outlet of the catchment were found for atrazine (i.e., approximately 8 microg L(-1) for a short period (<2 h) due to point source losses and between 1 and 3.5 microg L(-1) during more than 24 h due to diffuse losses).     

Online monitoring of molecular processes in a plasma air purifying system

Plasma air purifying systems present an interesting alternative to filters for purifying air. In this study, molecular processes in a commercially available ac driven plasma air purifier were studied in detail. This air purifier is supposed to reduce all air contaminants to small nontoxic molecules (e.g., H(2)O and CO(2)). However, degradation mechanisms are not yet fully understood. In this study, we investigated the exhaust of the plasma air purifier to determine which degradation products are formed. An interface was designed and constructed to allow the direct coupling of the plasma air purifier's exhaust to a mass spectrometer. The compounds studied, primary and secondary amines, were introduced at a concentration of 1 ppmV. Contrary to our expectations, polymerization instead of degradation was observed. The higher the ac voltage applied (max. 9.0 kV) to the plasma air purifier, the higher the mass of the oligomer distribution. Side chain oxidation products as well as oligomers could be observed for all compounds tested. Starting with amines of low mass (m/z < 200), compounds of molecular masses above 1000 Da were observed in the plasma air purifier. Detailed analysis of the observed mass spectra as well as experiments with deuterated dibutylamine helped to unravel the mechanism taking place in the plasma air purifier. Nitrate anions generated in the plasma air purifier (presumably from N(2)) are proposed to form ionic clusters with protonated amines.