Nitrous oxide emissions (N 2 O) from agricultural land are spatially and temporally variable. Most emission measurements are made with small ( 1 m 2 area) static chambers. We used N 2 O chamber data collected from multiple field experiments across different geo-climatic zones in the UK and from a range of nitrogen treatments to quantify uncertainties associated with flux measurements. Data were analysed to assess the spatial variability of fluxes, the degree of linearity of headspace N 2 O accumulation and the robustness of using ambient air N 2 O concentrations as a surrogate for sampling immediately after closure (T 0 ). Data showed differences of up to more than 50-fold between the maximum and minimum N 2 O flux from five chambers within one plot on a single sampling occasion, and that reliability of flux measurements increased with greater numbers of chambers. In more than 90% of the 1970 cases where linearity of headspace N 2 O accumulation was measured (with four or more sampling points), linear accumulation was observed; however, where non-linear accumulation was seen this could result in a 26% under-estimate of the flux. Statistical analysis demonstrated that the use of ambient air as a surrogate for T 0 headspace samples did not result in any consistent bias in calculated fluxes. Spatial variability has the potential to result in erroneous flux estimates if not taken into account, and generally introduces a far larger uncertainty into the calculated flux (commonly orders of magnitude more) than any uncertainties introduced through reduced headspace sampling or assumption of linearity of headspace accumulation. Hence, when deploying finite resources, maximizing chamber numbers should be given priority over maximizing the number of headspace samplings per enclosure period.

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Two cores collected in 2001 and 2004 from Flanders Moss ombrotrophic peat bog in central Scotland were dated (14C, 210Pb) and analysed (ICP-OES, ICP-MS) to derive and compare the historical atmospheric deposition records of Sb and Pb over the past 2500 years. After correction, via Sc, for contributions from soil dust, depositional fluxes of Sb and Pb peaked from ca. 1920-1960 A.D., with >95% of the anthropogenic inventories deposited post-1800 A.D. Over the past two centuries, trends in Sb and Pb deposition have been broadly similar, with fluctuations in the anthropogenic Sb/Pb ratio reflecting temporal variations in the relative input from emission sources such as the mining and smelting of Pb ores (in which Sb is commonly present, as at Leadhills/Wanlockhead in southern Scotland), combustion of coal (for which the Sb/Pb ratio is approximately an order of magnitude greater than in Pb ores) and exhaust emissions (Pb from leaded petrol) and abrasion products from the brake linings (Sb from heat-resistant Sb compounds) of automobiles. The influence of leaded petrol has been most noticeable in recent decades, firstly through the resultant minima in Sb/Pb and 206Pb/207Pb ratios (the latter arising from the use of less radiogenic Australian Pb in alkylPb additives) and then, during its phasing out and the adoption of unleaded petrol, complete by 2000 A.D., the subsequent increase in both Sb/Pb and 206Pb/207Pb ratios. The extent of the 20th century maximum anthropogenic enrichment of Sb and Pb, relative to the natural Sc-normalised levels of the Upper Continental Crust, was similar at approximately 50- to 100-fold. Prior to 1800 A.D., the influence of metallurgical activities on Sb and Pb concentrations in the peat cores during both the Mediaeval and Roman/pre-Roman periods was discernible, small Sb and Pb peaks during the latter appearing attributable, on the basis of Pb isotopic composition, to the mining/smelting of Pb ores indigenous to Britain.

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Cores collected from ombrotrophic peat bogs in west central, east central, northeast and southwest Scotland were dated (14C, 210Pb) and analyzed (ICP‐OES, ICP‐MS) to derive and compare their historical records of atmospheric anthropogenic Pb deposition over the past 2500 years. On the basis of Pb isotopic composition (e.g., 206Pb/207Pb), clear indications of Pb contamination during the pre‐Roman/Roman, post‐Roman and medieval periods were attributed to the mining and smelting of Pb ores from Britain and elsewhere in Europe. Between the 17th and early 20th centuries, during the industrial period, the mining and smelting of indigenous Scottish Pb ores were the most important sources of anthropogenic Pb deposition at three of the sites. In contrast, at the most southerly site, influences from the use of both British Pb ores and imported Australian Pb ores (in more southern parts of Britain) since the late 19th century were evident. At each of the sites, Australian‐Pb‐influenced car exhaust emissions (from the 1930s to late 1990s), along with significant contributions from coal combustion (until the late 1960s and onset of the postindustrial period), were evident. Atmospheric anthropogenic Pb deposition across Scotland was greatest (∼10 to 40 mg m−2 a−1) between the late 1880s and late 1960s, increasing southward, declining to 0.44 to 5.7 mg m−2 a−1 by the early 2000s. The records from four peat bogs extend knowledge of the chronology of atmospheric Pb deposition trends across the northern hemisphere, there being general agreement with other environmental archive records from not only Scotland but also other countries in western Europe and Greenland. Nevertheless, during all periods investigated here, the isotopic composition of atmospheric Pb deposition across western Europe and Greenland exhibited variations in the relative importance of different sources of anthropogenic Pb, as well as some differences in timings and magnitudes of anthropogenic Pb contamination, arising from variations in local and regional sources of Pb deposition and possibly climatic regimes.