High frequency UV-Vis sensors estimate error in riverine dissolved organic carbon load estimates from grab sampling.

High frequency ultraviolet - visible (UV-VIS) sensors offer a way of improving dissolved organic carbon (DOC) load estimates in rivers as they can be calibrated to DOC concentration. This is an improvement on periodic grab sampling, or the use of pumped sampling systems which store samples in-field before collection. We hypothesised that the move to high frequency measurements would increase the load estimate based on grab sampling due to systemic under-sampling of high flows. To test our hypotheses, we calibrated two sensors in contrasting catchments (Exe and Bow Brook, UK) against weekly grab sampled DOC measurements and then created an hourly time series of DOC for the two sites. Taking this measurement as a 'true' value of DOC load, we simulated 1,000 grab sampling campaigns at weekly, fortnightly and monthly frequency to understand the likely distribution of load and error estimates. We also performed an analysis of daily grab samples collected using a pumped storage sampling system with weekly collection. Our results show that: a) grab sampling systemically underestimates DOC loads and gives positively skewed distributions of results, b) this under-estimation and positive skew decreases with increasing sampling frequency, c) commonly used estimates of error in the load value are also systemically lowered by the oversampling of low, stable flows due to their dependence on the variance in the flow-weighted mean concentration, and d) that pumped storage systems may lead to under-estimation of DOC and over estimation of specific ultra-violet absorbance (SUVA), a proxy for aromaticity, due to biodegradation during storage.

Sources of dissolved organic carbon (DOC) in a mixed land use catchment (Exe, UK).

Many catchment management schemes in the UK have focussed on peatland restoration to improve ecosystem services such as carbon sequestration, water quality and biodiversity. The effect of these schemes on dissolved organic carbon (DOC) flux is critical in understanding peatland carbon budgets as well as the implications for drinking water treatment. In many catchments, however, peatland areas are not the only source of DOC, meaning that their significance at the full catchment scale is unclear. In this paper we have evaluated the importance of different land uses as sources of DOC by combining three datasets obtained from the Exe catchment, UK. The first dataset comprises a weekly monitoring record at three sites for six years, the second, a monthly monitoring record of 25 sites in the same catchment for one year, and the third, an assessment of DOC export from litter and soil carbon stocks. Our results suggest that DOC concentration significantly increased from the peaty headwaters to the mixed land-use areas (ANOVA F = 12.52, p < 0.001, df = 2), leading to higher flux estimates at the downstream sites. We present evidence for three possible explanations: firstly, that poor sampling of high flows may lead to underestimation of DOC flux, second, that there are significant sources of DOC besides the peatland headwaters, and finally, that biological- and photo-degradation decreases the influence of upstream DOC sources. Our results provide evidence both for the targeting of catchment management in peatland areas as well as the need to consider DOC from agricultural and forested areas of the catchment.

The impact of climate change on the treatability of dissolved organic matter (DOM) in upland water supplies: a UK perspective.

Climate change in the UK is expected to cause increases in temperatures, altered precipitation patterns and more frequent and extreme weather events. In this review we discuss climate effects on dissolved organic matter (DOM), how altered DOM and water physico-chemical properties will affect treatment processes and assess the utility of techniques used to remove DOM and monitor water quality. A critical analysis of the literature has been undertaken with a focus on catchment drivers of DOM character, removal of DOM via coagulation and the formation of disinfectant by-products (DBPs). We suggest that: (1) upland catchments recovering from acidification will continue to produce more DOM with a greater hydrophobic fraction as solubility controls decrease; (2) greater seasonality in DOM export is likely in future due to altered precipitation patterns; (3) changes in species diversity and water properties could encourage algal blooms; and (4) that land management and vegetative changes may have significant effects on DOM export and treatability but require further research. Increases in DBPs may occur where catchments have high influence from peatlands or where algal blooms become an issue. To increase resilience to variable DOM quantity and character we suggest that one or more of the following steps are undertaken at the treatment works: a) 'enhanced coagulation' optimised for DOM removal; b) switching from aluminium to ferric coagulants and/or incorporating coagulant aids; c) use of magnetic ion-exchange (MIEX) pre-coagulation; and d) activated carbon filtration post-coagulation. Fluorescence and UV absorbance techniques are highlighted as potential methods for low-cost, rapid on-line process optimisation to improve DOM removal and minimise DBPs.