Mechano-chemical manipulation of Sn chains on Si(1 0 0) by NC-AFM.

We investigate the atomic structure of Sn dimer chains grown on the Si(1 0 0) surface using non-contact atomic force microscopy (NC-AFM) at cryogenic temperatures. We find that similar to the native Si(1 0 0) dimer structure, the ground state of the Sn dimer structure is buckled at low temperature. At 5 K we show that the buckling state of the Sn dimers may be controllably, and reversibly, manipulated with atomic precision by close approach of the tip, without modification of the underlying substrate buckling structure. At intermediate cryogenic temperatures we observe changes in the configuration of the dimer chains in the region where the tip-sample interaction is very weak, suggesting that the energy barrier to transit between configurations is sufficiently small to be surmounted at 78 K.

Simulated structure and imaging of NTCDI on Si(1 1 1)-7 × 7 : a combined STM, NC-AFM and DFT study.

The adsorption of naphthalene tetracarboxylic diimide (NTCDI) on Si(1 1 1)-7 × 7 is investigated through a combination of scanning tunnelling microscopy (STM), noncontact atomic force microscopy (NC-AFM) and density functional theory (DFT) calculations. We show that NTCDI adopts multiple planar adsorption geometries on the Si(1 1 1)-7 × 7 surface which can be imaged with intramolecular bond resolution using NC-AFM. DFT calculations reveal adsorption is dominated by covalent bond formation between the molecular oxygen atoms and the surface silicon adatoms. The chemisorption of the molecule is found to induce subtle distortions to the molecular structure, which are observed in NC-AFM images.

Mapping the force field of a hydrogen-bonded assembly.

Hydrogen bonding underpins the properties of a vast array of systems spanning a wide variety of scientific fields. From the elegance of base pair interactions in DNA to the symmetry of extended supramolecular assemblies, hydrogen bonds play an essential role in directing intermolecular forces. Yet fundamental aspects of the hydrogen bond continue to be vigorously debated. Here we use dynamic force microscopy (DFM) to quantitatively map the tip-sample force field for naphthalene tetracarboxylic diimide molecules hydrogen-bonded in two-dimensional assemblies. A comparison of experimental images and force spectra with their simulated counterparts shows that intermolecular contrast arises from repulsive tip-sample interactions whose interpretation can be aided via an examination of charge density depletion across the molecular system. Interpreting DFM images of hydrogen-bonded systems therefore necessitates detailed consideration of the coupled tip-molecule system: analyses based on intermolecular charge density in the absence of the tip fail to capture the essential physical chemistry underpinning the imaging mechanism.

Field-testing a new directional passive air sampler for fugitive dust in a complex industrial source environment.

Quantifying the sources of fugitive dusts on complex industrial sites is essential for regulation and effective dust management. This study applied two recently-patented Directional Passive Air Samplers (DPAS) to measure the fugitive dust contribution from a Metal Recovery Plant (MRP) located on the periphery of a major steelworks site. The DPAS can collect separate samples for winds from different directions (12 × 30° sectors), and the collected dust may be quantified using several different measurement methods. The DPASs were located up and down-prevailing-wind of the MRP processing area to (i) identify and measure the contribution made by the MRP processing operation; (ii) monitor this contribution during the processing of a particularly dusty material; and (iii) detect any changes to this contribution following new dust-control measures. Sampling took place over a 12-month period and the amount of dust was quantified using photographic, magnetic and mass-loading measurement methods. The DPASs are able to effectively resolve the incoming dust signal from the wider steelworks complex, and also different sources of fugitive dust from the MRP processing area. There was no confirmable increase in the dust contribution from the MRP during the processing of a particularly dusty material, but dust levels significantly reduced following the introduction of new dust-control measures. This research was undertaken in a regulatory context, and the results provide a unique evidence-base for current and future operational or regulatory decisions.

Precise orientation of a single C60 molecule on the tip of a scanning probe microscope.

We show that the precise orientation of a C(60) molecule which terminates the tip of a scanning probe microscope can be determined with atomic precision from submolecular contrast images of the fullerene cage. A comparison of experimental scanning tunneling microscopy data with images simulated using computationally inexpensive Hückel theory provides a robust method of identifying molecular rotation and tilt at the end of the probe microscope tip. Noncontact atomic force microscopy resolves the atoms of the C(60) cage closest to the surface for a range of molecular orientations at tip-sample separations where the molecule-substrate interaction potential is weakly attractive. Measurements of the C(60)-C(60) pair potential acquired using a fullerene-terminated tip are in excellent agreement with theoretical predictions based on a pairwise summation of the van der Waals interactions between C atoms in each cage, i.e., the Girifalco potential [L. Girifalco, J. Phys. Chem. 95, 5370 (1991)].

Imaging and manipulation of the Si(100) surface by small-amplitude NC-AFM at zero and very low applied bias.

We use a noncontact atomic force microscope in the qPlus configuration to investigate the structure and influence of defects on the Si(100) surface. By applying millivolt biases, simultaneous tunnel current data is acquired, providing information about the electronic properties of the surface at biases often inaccessible during conventional STM imaging, and highlighting the difference between the contrast observed in NC-AFM and tunnel current images. We also show how NC-AFM (in the absence of tunnel current) can be used to manipulate both the clean c(4 × 2) surface and dopant-related defects.

Estimating overall persistence and long-range transport potential of persistent organic pollutants: a comparison of seven multimedia mass balance models and atmospheric transport models.

Two different approaches to modeling the environmental fate of organic chemicals have been developed in recent years. The first approach is applied in multimedia box models, calculating average concentrations in homogeneous boxes which represent the different environmental media, based on intermedia partitioning, transport, and degradation processes. In the second approach, used in atmospheric transport models, the spatially and temporally variable atmospheric dynamics form the basis for calculating the environmental distribution of chemicals, from which also exchange processes to other environmental media are modeled. The main goal of the present study was to investigate if the multimedia mass balance models CliMoChem, SimpleBox, EVn-BETR, G-CIEMS, OECD Tool and the atmospheric transport models MSCE-POP and ADEPT predict the same rankings of the overall persistence (P(ov)) and long-range transport potential (LRTP) of POPs, and to explain differences and similarities between the rankings by the mass distributions and inter-compartment mass flows. The study was performed for a group of 14 reference chemicals. For P(ov), the models yield consistent results, owing to the large influence of phase partitioning parameters and degradation rate constants, which are used similarly by all models. Concerning LRTP, there are larger differences between the models than for P(ov), due to different LRTP calculation methods and spatial model resolutions. Between atmospheric transport models and multimedia fate models, no large differences in mass distributions and inter-compartment flows can be recognized. Deviations in mass flows are mainly caused by the geometrical design of the models.

Field deployment of thin film passive air samplers for persistent organic pollutants: a study in the urban atmospheric boundary layer.

This paper reports on the first field deployment of rapidly equilibrating thin-film passive air samplers under ambient conditions. The POlymer-coated Glass (POG) samplers have a coating of ethylene vinyl acetate (EVA) less than 1 microm thick applied to a glass surface. This can be dissolved off after exposure and prepared for the quantification of persistent organic pollutants (POPs) that have partitioned into the film during field exposure. In this study, POGs were deployed at various heights on the CN Tower in Toronto, Canada, to investigate the vertical distribution of selected compounds (PCBs, PAHs, organochlorine pesticides) in the atmospheric boundary layer of an urban area. The feasibility of the method to detect POPs from a few cubic meters of air was demonstrated, indicating the potential for rapid, low-volume sampling of air for ambient levels of POPs. PAH levels declined sharply with height, confirming ground-level emissions in urban areas as sources of these compounds; PCBs did the same, although less strongly. Different sampling events detected different vertical distributions of OC pesticides which could be related to local or distantsources, and variations in POPs on the samplers in these different events/heights demonstrate the dynamic nature of sources and atmospheric mixing of POPs.

Field calibration of rapidly equilibrating thin-film passive air samplers and their potential application for low-volume air sampling studies.

This paper reports on a field calibration and ambient deployment study with rapidly equilibrating thin-film passive air samplers. POlymer-coated Glass (POG) samplers have a coating of ethylene vinyl acetate (EVA) less than 1 microm thick coated on to glass, which can be dissolved off after exposure and prepared for quantification of persistent organic pollutants (POPs) that have partitioned into the film during field exposure. In this study, POGs were exposed for up to 18 d, in a study to assess compound uptake rates and their time to approach equilibrium. Results confirmed theoretical predictions, with time to equilibrium varying between a few hours to ca. 20 d for PCB-18 and PCB-138, respectively. Performance reference compounds and contaminated POGs were used to investigate depuration kinetics, confirming that lighter congeners behave extremely dynamically with substantial losses from the films over periods of a few hours. Repeated deployments of the samplers for different3-d periods yielded detectable levels of a range of PCB congeners, which had partitioned from as little as approximately 2 to 10 m3 air. This highlights the potential utility of POGs for extremely sensitive and dynamic passive air sampling in the future to help improve understanding of sources, environmental fate, and behavior of POPs. Recommendations are made for future improvements/refinements in POG sampling and handling procedures.

The maximum reservoir capacity of soils for persistent organic pollutants: implications for global cycling.

The concept of maximum reservoir capacity (MRC), the ratio of the capacities of the surface soil and of the atmospheric mixed layer (AML) to hold chemical under equilibrium conditions, is applied to selected persistent organic pollutants (POPs) in the surface 'skin' (1 mm) of soils. MRC is calculated as a function of soil organic matter (SOM) content and temperature-dependent K(OA) and mapped globally for selected PCB congeners (PCB-28; -153; -180) and HCB, to identify regions with a higher tendency to retain POPs. It is shown to vary over many orders of magnitude, between compounds, locations and time (seasonally/diurnally). The MRC approach emphasises the very large capacity of soils as a storage compartment for POPs. The theoretical MRC concept is compared to reality and its implications for the global cycling of POPs are discussed. Sharp gradients in soil MRC can exist in mountainous areas and between the land and ocean. Exchanges between oceans and land masses via the atmosphere is likely to be an important driver to the global cycling of these compounds, and net ocean-land transfers could occur in some areas.

European-scale modeling of concentrations and distribution of polybrominated diphenyl ethers in the pentabromodiphenyl ether product.

The results from a modeling exercise utilizing the European variant (EVn) BETR multimedia environmental fate model are presented for selected polybrominated diphenyl ethers (PBDEs) of the technical penta- (Pe-) bromodiphenyl ether (BDE) product. The objectives of this study were to test PeBDE emission estimates from the literature for Europe by investigating the consistency between model predictions and ambient measurements to address the ability of the model to predict spatial variability and differences between congeners. Concurrently sampled and analyzed passive sampling air data, together with soil and grass data, were used as key model validation tools. The model steady-state simulations gave generally good agreement with measured data for BDE-47 and -99 with greater discrepancies for heavier congeners (e.g., BDE-153). To predict future atmospheric concentration trends, the model was used in its fully dynamic mode over the period 1970--2010. It was predicted that atmospheric concentrations peaked around 1997, declining with an overall "disappearance" half-life of 4.8 years. Soil and grass levels were underestimated by the model; possible reasons for differences with measurement data are further explored. Finally, the importance of temporally and spatially resolved environmental data sets is highlighted, while improved quantification of degradation half-lives is essential to better understand and predict the behavior of BDE congeners in PeBDE.

Estimation of the production, consumption, and atmospheric emissions of pentabrominated diphenyl ether in Europe between 1970 and 2000.

A European consumption and atmospheric emissions inventory for pentabrominated diphenyl ethers (PeBDEs) is derived for the period 1970-2000. This time frame has seen a rise in the widespread usage of PeBDE, followed by more recent restrictions/bans. It is estimated that a total of 3000-5000 t of PeBDEs was produced in Europe during this period, with a further 9000-10,000 t imported in finished articles. The main uses for PeBDE are to flame retard consumer products as well as in packaging and solid elastomers. Their major stocks are predicted to be in polyurethane (flexible) foams with up to 30% in cars; more than 10% in furniture foam; and the rest in textiles, building material, packaging, and solid applications. Release of PeBDEs from treated products into environmental media are estimated with a focus on atmospheric inputs via volatilization from their use in cars, upholstered furniture, textiles, television sets, personal computers, and other recycled material. Different emission factors are used to derive different emission scenarios. A peak in atmospheric emissions of between 22 and 31 t of BDE-47 is estimated to have occurred around 1997, with a decline of approximately 20% in 2000. Comparisons with long-term environmental monitoring data revealed that the time trends of human blood and milk concentrations follow similar patterns to the generated emissions, while sediment core levels increase more slowly, probably because they respond to a mix of atmospheric and catchment inputs. The emissions data derived here can be used in a spatially and temporally resolved form as input data for multi-media environmental fate modeling.

Atmospheric emissions of polybrominated diphenyl ethers and other persistent organic pollutants during a major anthropogenic combustion event.

Air samples were taken for the analysis of persistent organic pollutants before, during, and after the national U.K. "Bonfire Festival" in November 2000. As expected, ambient levels of polynuclear aromatic hydrocarbons (PAHs) increased sharply in response to the widespread diffusive combustion processes that occurred at the time. Polybrominated diphenyl ethers (PBDEs) also increased at the suburban sampling location, to a greater extent than the PAHs. The rise and fall in PBDE concentrations was rapid, coinciding closely with the PAH "combustion markers". These data provide evidence for a novel mechanism responsible for dissipation of PBDEs into the environment. It is hypothesized that products treated with the penta-BDE product--notably household furnishing foams and textiles--have been subject to (unsanctioned) burning on private bonfires; even if the majority of the PBDE burden of such products is debrominated/broken down in the fires, it is shown that only small amounts of the total "stock" of penta product need be emitted to generate the concentrations detected. The mixture of PBDEs in the air during the Bonfire Festival was enriched in higher brominated congeners (e.g., BDE-99, -153, and -154) compared to that in background air. Estimates are made of the masses of compound classes that may have been emitted to the atmosphere during the festival.

Global distribution and budget of PCBs and HCB in background surface soils: implications for sources and environmental processes.

This paper presents data from a survey of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) concentrations in 191 global background surface (0-5 cm) soils. Differences of up to 4 orders of magnitude were found between sites for PCBs. The lowest and highest PCB concentrations (26 and 97,000 pg/g dw) were found in samples from Greenland and mainland Europe (France, Germany, Poland), respectively. Background soil PCB concentrations were strongly influenced by proximity to source region and soil organic matter (SOM) content Most (>80%) of the estimated soil PCB burden remains in the "global source region" of the Northern Hemisphere (NH) temperate latitudes (30-60 degrees N) or in the OM-rich soils just north of that %SOM correlated with PCB and HCB in the global data set, with the correlation coefficients being greater for HCB and the lighter PCBs than for heavier homologues. OM-rich soils in the NH consistently contained the highest burdens; such soils are a key global compartment for these compounds. Evidence for global fractionation of PCBs was found in the subset of soils from latitudes north of the global source region but was not discerned with the global data set The full data set was used to estimate the burden for individual congeners/homologues in surface background soils and a global soil total PCB burden of 21,000 t. The significance of the inventory is briefly discussed in relation to the latest estimates of global production and atmospheric emission.

A congener-specific PCDD/F emissions inventory for the UK: do current estimates account for the measured atmospheric burden?

Considerable effort has been expended in the UK and elsewhere to quantify and rank PCDD/F primary sources and emissions to the environment, principally the atmosphere, so that cost-effective source reduction measures can be taken. Here, we predict a congener-specific emissions inventory for primary and secondary nondioxin-regulated sources to the UK atmosphere, estimated to have ranged from 3 to 22 kg in 1996. The inventory profile is dominated by OCDD (approximately 30-40%), 1,2,3,4,6,7,8-HpCDD (approximately 15-19%) and 1,2,3,4,6,7,8-HpCDF (approximately 14-19%). Congeners 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD dominate the sigmaTEQ composition. Mass balance modelling suggests that the predicted congener pattern in UK air (based on the emission inventory) is similar to observed measurements, with absolute concentrations being estimated within a factor of 2 for most congeners. Calculations taking into account atmospheric weathering processes and long range (advective) transport suggest that PCDD/F sources to ambient air are primarily ongoing and that atmospheric mixing will mask individual emission source profiles/identities. This supports measured evidence for the consistency of PCDD/F air profiles observed around the UK throughout the year.

A generic model of human lifetime exposure to persistent organic contaminants: development and application to PCB-101.

We have developed a model which successfully reconstructs the lifetime polychlorinated biphenyl (PCB)-101 burden of the UK population for individuals born between 1920 and 1980. It not only follows burdens and clearance of persistent organic contaminants throughout a human lifetime--taking changes in age and body composition into account--but also, importantly, incorporates changing environmental concentrations of the compound of interest. Predicted results agree well with available measured lipid concentrations in human tissues. Its unique construction takes into account both changing environmental concentrations of PCBs in principal food groups and changing dietary habits during the time period. Because environmental burdens of persistent organic contaminants have changed over the last 60 years, residues in food will also have mirrored this change. Critically in this respect, the year in which an individual was born determines the shape and magnitude of their exposure profile for a given compound. Observed trends with age represent an historical legacy of exposure and are not simply a function of equal yearly cumulative inputs. We can demonstrate that the release profile of PCB-101 controls levels in the food supply and ultimately the burden of individuals throughout their life. This effect is expected to be similar for other PCB congeners and persistent organic compounds such as polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). Models of this type have important applications as predictive tools to estimate the likely impact of source-reduction strategies on human tissue concentrations.

Human exposure to PCDD/Fs in the UK: the development of a modelling approach to give historical and future perspectives.

In order to assess the long-term impact of persistent organic contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) it is important to be able to quantify historical exposure. An understanding of past exposure is not only important to place our current body burdens in perspective, but is useful in assessing our potential future exposure. Unfortunately, very few direct measurements of our main source of exposure (i.e., food) over the past decades are available. This study attempts to reconstruct the historical exposure of the UK population to PCDD/Fs using a combination of emission estimates, information on environmental temporal trends derived from sediment cores and archived materials, and environmental/human fate modelling. Predicted adipose and blood lipid concentrations for a typical cross section of the population are derived over time (1920-2000), which is compared with measured data. The approach has been tested with two PCDDs and two PCDFs and showed encouraging agreement with measured data. Certain parts of the modelling methodology have been highlighted where there is still poor understanding of the processes governing fate and behaviour. These areas are discussed and recommendations for future improvements are made. The paper thus represents an initial modelling approach which defines both the historical (1920-present) and future (present-2020) fate of PCDD/Fs in the UK population.

Metabolism and body-burden of PCBs in lactating dairy cows.

This paper uses data from a detailed 4 month PCB mass balance study on lactating cows fed a naturally contaminated background diet to quantify the metabolism and body-burdens of a range of PCB congeners. Dietary intake fluxes and milk and faecal output fluxes reported previously are combined with subcutaneous fat and blood PCB concentrations and with data from tissue/organ samples from a slaughtered animal to estimate the degree of metabolism within the cow. A total body burden is derived, showing that fat deposits account for approximately 98% of total PCB present in the lactating cow. The daily intake through feed (ng day-1) accounted for between 0.9 and 1.5% of the total body burden for persistent congeners (e.g. PCB 153) and up to 43% for those congeners which are readily metabolised (e.g. PCB 52). Detailed balances for a range of tri- to octa-chlorinated PCBs are presented and clearly demonstrate that many congeners are metabolised effectively by lactating dairy cows (e.g. PCB 149) whilst others are efficiently transferred to human dairy food products. An approach to predicting the degree of metabolism for individual PCB congeners is presented which gives good agreement with observations.

Assessment of organic contaminant fate in waste water treatment plants. I: Selected compounds and physicochemical properties.

An extensive and comprehensive literature review has been conducted for compounds which we hypothesise could be present in sludge and maintain their integrity following application to agricultural land. The following compounds have been selected for review; chlorinated paraffins, quintozene, brominated diphenyl ethers, polychlorinated naphthalenes, polydimethylsiloxanes, chloronitrobenzenes, and a range of biologically active and pharmaceutical compounds. All have received interest as a result of their persistence and/or toxicity in environmental media. Physicochemical property information has also been compiled and/or calculated. In this way, an accompanying paper will attempt to predict compound fate in waste water treatment plants (WWTPs) and assess likely transfers from soil/plants to grazing livestock. These papers describe a first attempt to predict the fate of these classes of compounds in the environment and prioritise those of greatest concern.