Excessive riverine nutrient concentrations threaten aquatic ecosystem structure and functioning and can pose substantial risks to human health. Robust monitoring strategies are therefore required to ...generate reliable estimates of river nutrient loads and to improve understanding of the catchment processes that drive nutrient fluxes. Furthermore, these data are vital for prediction of future trends under changing environmental conditions and thus the development of appropriate mitigation measures. In recent years, technological developments have led to an increase in the use of in-situ nutrient analysers, which enable measurements at far higher temporal resolutions than can be achieved with discrete sampling and subsequent laboratory analysis. In this paper, we review the principles underlying the key techniques used for in-situ nutrient monitoring and highlight both the advantages, opportunities and challenges associated with high-resolution sampling programs. We then suggest how adaptive monitoring strategies, comprising several different temporal sample frequencies, controlled by one or more ‘trigger variables’ (e.g. river stage, turbidity, or nutrient concentration), can advance our understanding of catchment nutrient dynamics while simultaneously overcoming many of the practical and economic challenges encountered in typical in-situ river nutrient monitoring applications. We present examples of short-term variability in river nutrient dynamics, driven by complex catchment behaviour, which support our case for the development of monitoring systems that can adapt in real-time to rapid changes in environmental conditions. Finally, we suggest future research directions based on emerging technologies in this field.
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•In-situ river nutrient monitoring offers new insights into catchment processes.•Real-time adaptive sampling provides data during biogeochemically active periods.•This approach captures hot moments in nutrient dynamics and reduces data redundancy.•New technologies may increase the coverage of nutrient sensors in river catchments.
The role that hydrology plays in governing the interactions between dissolved organic carbon (DOC) and nitrogen in rivers draining lowland, agricultural landscapes is currently poorly understood. In ...light of the potential changes to the production and delivery of DOC and nitrate to rivers arising from climate change and land use management, there is a pressing need to improve our understanding of hydrological controls on DOC and nitrate dynamics in such catchments. We measured DOC and nitrate concentrations in river water of six reaches of the lowland river Hampshire Avon (Wiltshire, southern UK) in order to quantify the relationship between BFI (BFI) and DOC : nitrate molar ratios across contrasting geologies (Chalk, Greensand, and clay). We found a significant positive relationship between nitrate and BFI (p < 0. 0001), and a significant negative relationship between DOC and BFI (p < 0. 0001), resulting in a non-linear negative correlation between DOC : nitrate molar ratio and BFI. In the Hampshire Avon, headwater reaches which are underlain by clay and characterized by a more flashy hydrological regime are associated with DOC : nitrate ratios > 5 throughout the year, whilst groundwater-dominated reaches underlain by Chalk, with a high BFI have DOC : nitrate ratios in surface waters that are an order of magnitude lower (< 0.5). Our analysis also reveals significant seasonal variations in DOC : nitrate transport and highlights critical periods of nitrate export (e.g. winter in sub-catchments underlain by Chalk and Greensand, and autumn in drained, clay sub-catchments) when DOC : nitrate molar ratios are low, suggesting low potential for in-stream uptake of inorganic forms of nitrogen. Consequently, our study emphasizes the tight relationship between DOC and nitrate availability in agricultural catchments, and further reveals that this relationship is controlled to a great extent by the hydrological setting.
Rationale
Plastic mulch film manages weed growth and moisture loss on the surface of cropping beds. The chemical components of such plastics include polymer(s), additives and non‐intentionally added ...substances (NIASs). The unknown chemical nature and behaviours of these constituents require investigation due to their potential to add to the anthropogenic chemical burden in the agrifood system.
Methods
Solvent extracts of a commercial 15% polylactic acid (PLA)/85% poly(butylene adipate‐co‐terephthalate) mulch film were investigated using gas chromatography–mass spectrometry (GC–MS) with electron ionisation to characterise the additive and NIAS components. The obscurity of some of the NIASs meant their identification was not readily achieved through routine MS library comparisons. As such, the identification of several polymer‐derived compounds required interpretation of the MS data and re‐application of the derived fragmentation patterns with reference to the wider literature. Unknowns were confirmed using commercially available compounds.
Results
Unknown NIASs were identified as cyclic oligoesters comprised of the monomeric building blocks of the polymer system. Cyclic structures derived from the monomers of polybutylene adipate (PBA) and polybutylene terephthalate (PBT) fragmented through a primary pathway involving 1,5‐ and 1,3‐H transfers at ester linkages. Characteristic ions at m/z 111, 129, 183 and 201 for PBA‐derived cyclic oligoesters and m/z 104, 132, 149 and 221 for PBT‐derived cyclic oligoesters were assigned in the mass spectra of unknowns. Cyclic oligoesters containing sebacate moieties were also identified, indicating the presence of polybutylene sebacate as an unexpected component of the mulch.
Conclusions
Systematic analyses of the sort reported here are valuable for providing alternative approaches for the identification of plastic‐related chemicals. Open publication of MS spectral data is required to build a greater understanding of the mulch film chemical components contributing to the environmental chemical load introduced to agroecosystems.
Micro and macroplastics are emerging contaminants in agricultural settings, yet their impact on nitrogen (N) cycling and partitioning in plant-soil-microbial systems is poorly understood. In this ...mesocosm-scale study, spring barley (Hordeum vulgare L.) was exposed to macro or microplastic produced from low density polyethylene (LDPE) or biodegradable plastic at concentrations equivalent to 1, 10 and 20 years of plastic mulch film use. Partitioning of 15N-labelled fertiliser into plant biomass, soil and leachate yielded a partial mass balance. Soil N partitioning was probed via compound-specific 15N-stable isotope analyses of soil microbial protein. Concentration-dependent decreases in plant 15N uptake occurred with increased leached nitrogen for LDPE microplastic. Assimilation into soil microbial protein was higher for biodegradable plastics, which we associate with early-stage biodegradable plastic degradation. Partitioning of 15N into inorganic soil N pools was affected by LDPE size, with lower assimilation into the microbial protein pool. While microplastics and macroplastics altered soil N cycling, the limited impacts on plant health indicated the threshold for negative effects was not reached at agriculturally relevant concentrations. This study highlights the difference between conventional and biodegradable plastics, and emphasises that the interplay of micro and macroplastics on soil N cycling must be considered in future studies.
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•Barley was exposed to biodegradable and LDPE macro and microplastic.•15N-tracing indicated LDPE microplastic reduced plant 15N uptake due to N losses.•LDPE plastics altered partitioning of 15N within soil N pools.•Biodegradable macro and micro plastic increased microbial N uptake.•Biodegradable and LDPE plastics had differing impacts on plant-soil N partitioning.
Rationale
Anthropogenic organic inputs to freshwaters can exert detrimental effects on aquatic ecosystems, raising growing concern for both environmental conservation and water security. Current ...regulation by the EU water framework directive (European Union, 2000/60/EC) relates to organic pollution by monitoring selected micropollutants; however, aquatic ecosystem responses require a comprehensive understanding of dissolved organic matter (DOM) composition. The introduction of high‐resolution mass spectrometry (HRMS) is set to greatly increase our understanding of the composition of DOM of both natural and anthropogenic origin derived from diffuse and point sources.
Methods
DOM was extracted from riverine and treated sewage effluent using solid‐phase extraction (SPE) and analysed using dissolved organic carbon analysis, direct‐infusion high‐resolution mass spectrometry (DI‐HRMS) and high‐performance liquid chromatography (HPLC)/HRMS. The data obtained were analysed using univariate and multivariate statistics to demonstrate differences in background DOM, anthropogenic inputs and in‐river mixing. Compound identifications were achieved based on MS2 spectra searched against on‐line databases.
Results
DI‐HRMS spectra showed the highly complex nature of all DOM SPE extracts. Classification and visualisation of extracts containing many thousands of individual compounds were achieved using principal component analysis (PCA) and hierarchical cluster analysis. Kruskal‐Wallis analyses highlighted significant discriminating ions originating from the sewage treatment works for more in‐depth investigation by HPLC/HRMS. The generation of MS2 spectra in HPLC/HRMS provided the basis for identification of anthropogenic compounds including; pharmaceuticals, illicit drugs, metabolites and oligomers, although many thousands of compounds remain unidentified.
Conclusions
This new approach enables comprehensive analysis of DOM in extracts without any preconceived ideas of the compounds which may be present. This approach has the potential to be used as a high throughput, qualitative, screening method to determine if the composition of point sources differs from that of the receiving water bodies, providing a new approach to the identification of hitherto unrecognised organic contribution to water bodies.
The dynamic interactions between dissolved organic matter (DOM) and particulate organic matter (POM) are central in nutrient cycling in freshwater ecosystems. However, the molecular-level mechanisms ...of such interactions are still poorly defined. Here, we study spatial differences in the chemical (i.e., individual proteinaceous amino acids) and microbial (i.e., 16S rRNA) composition of suspended sediments in the River Chew, UK. We then applied a compound-specific stable isotope probing (SIP) approach to test the potential assimilation of
13
C,
15
N-glutamate (Glu) and
15
N-NO
3
−
into proteinaceous biomass by particle-associated microbial communities over a 72-h period. Our results demonstrate that the composition of suspended particles is strongly influenced by the effluent of sewage treatment works. Fluxes and percentages of assimilation of both isotopically labelled substrates into individual proteinaceous amino acids showed contrasting dynamics in processing at each site linked to primary biosynthetic metabolic pathways. Preferential assimilation of the organic molecule glutamate and evidence of its direct assimilation into newly synthesised biomass was obtained. Our approach provides quantitative molecular information on the mechanisms by which low molecular weight DOM is mineralised in the water column compared to an inorganic substrate. This is paramount for better understanding the processing and fate of organic matter in aquatic ecosystems.
Over the last 50 years, the intense use of agricultural plastic in the form of mulch films has led to an accumulation of plastic in soil, creating a legacy of plastic in agricultural fields. Plastic ...often contains additives, however it is still largely unknown how these compounds affect soil properties, potentially influencing or masking effects of the plastic itself. Therefore, the aim of this study was to investigate the effects of pure plastics of varying sizes and concentrations, to improve our understanding of plastic-only interactions within soil-plant mesocosms. Maize (Zea mays L.) was grown over eight weeks following the addition of micro and macro low-density polyethylene and polypropylene at increasing concentrations (equivalent to 1, 10, 25, and 50 years mulch film use) and the effects of plastic on key soil and plant properties were measured. We found the effect of both macro and microplastic on soil and plant health is negligible in the short-term (1 to <10 years). However, ≥ 10 years of plastic application for both plastic types and sizes resulted in a clear negative effect on plant growth and microbial biomass. This study provides vital insight into the effect of both macro and microplastics on soil and plant properties.
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•Crop height and nutrient content decreased with increasing plastic concentration.•Soil moisture content severely reduced with increasing plastic concentration.•Changes in soil & plant properties were more pronounced in microplastic treatments.•Effects of plastic addition are negligible in the short term for low concentrations.•Microbial biomass decreased with increasing plastic concentration.
Dissolved organic matter (DOM) plays an important role in freshwater biogeochemistry. To investigate the influence of catchment character on the quality and quantity of DOM in freshwaters, 45 ...sampling sites draining subcatchments of contrasting soil type, hydrology, and land cover within one large upland-dominated and one large lowland-dominated catchment were sampled over a 1-yr period. Dominant land cover in each subcatchment included: arable and horticultural, blanket peatland, coniferous woodland, and improved, unimproved, acid, and calcareous grasslands. The composition of the C, N, and P pool was determined as a function of the inorganic nutrient species (NO₃⁻, NO₂⁻, NH₄⁺, and PO₄3−) and dissolved organic nutrient (dissolved organic carbon DOC, dissolved organic nitrogen DON, and dissolved organic phosphorus DOP) concentrations. DOM quality was assessed by calculation of the molar DOC : DON and DOC : DOP ratios and specific ultraviolet absorbance (SUVA254). In catchments with little anthropogenic nutrient inputs, DON and DOP typically composed > 80% of the total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations. By contrast, in heavily impacted agricultural catchments DON and DOP typically comprised 5–15% of TDN and 10–25% of TDP concentrations. Significant differences in DOC : DON and DOC : DOP ratios were observed between land cover class with significant correlations observed between both the DOC : DON and DOC : DOP molar ratios and SUVA254 (r
s = 0.88 and 0.84, respectively). Analysis also demonstrated a significant correlation between soil C : N ratio and instream DOC : DON/DOP (r
s = 0.79 and 0.71, respectively). We infer from this that soil properties, specifically the C : N ratio of the soil organic matter pool, has a significant influence on the composition of DOM in streams draining through these landscapes.
In fresh waters, the origins of dissolved organic matter (DOM) have been found to exert a fundamental control on its reactivity, and ultimately, its ecosystem functional role. A detailed ...understanding of landscape scale factors that control the export of DOM to aquatic ecosystems is, therefore, pivotal if the effects of DOM flux to fresh waters are to be fully understood. In this study we present data from a national sampling campaign across the United Kingdom in which we explore the variability in DOM composition in three broad landscape types defined by similar precipitation, geology, land use and management, hydrology, and nutrient enrichment status. We characterised samples from fifty-one sites, grouping them into one of three major underlying classifications: circumneutral streams underlain by clay and mudstone (referred to as ‘clay’), alkaline streams underlain by Cretaceous Chalk or by Carboniferous or Jurassic Limestone (‘limestone’), and acidic streams in peatland catchments underlain by a range of low permeability lithologies (‘peat’). DOM composition was assessed through organic matter stoichiometry (organic carbon: organic nitrogen; organic carbon: organic phosphorus; C/N(P)
DOM
) and metrics derived from ultra-violet (UV)/visible spectroscopic analysis of DOM such as specific UV absorption (a
254
nm; SUVA
254
). We found similar SUVA
254
, C/N
DOM
and DOM/a
254
relationships within classifications, demonstrating that despite a large degree of heterogeneity within environments, catchments with shared environmental character and anthropogenic disturbance export DOM with a similar composition and character. Improving our understanding of DOM characterisation is important to help predict shifts in stream ecosystem function, and ecological responses to enrichment or mitigation efforts and how these may result in species composition shifts and biodiversity loss in freshwater ecosystems.
Monitoring programmes worldwide use biota to assess the “health” of water bodies. Indices based on biota are used to describe the change in status of sites over time, to identify progress against ...management targets and to diagnose the causes of biological degradation. A variety of numerical stressor‐specific biotic indices have been developed based on the response of biota to differences in stressors among sites. Yet, it is not clear how variation in pressures within sites, over what time period, and in what combination has the greatest impact on different biotic groups. An understanding of how temporal variation in pressures influences biological assessment indices would assist in setting achievable targets and help focus catchment‐scale mitigation strategies to ensure that they deliver the desired improvements in biological condition.
Hydrochemical data provided by a network of high‐frequency (15 or 30 min) automated monitoring stations over 3 years were matched to replicated biological data to understand the influence of spatio‐temporal variation in pollution pressures on biological indices. Hydrochemical data were summarised in various ways to reflect central tendency, peaks, troughs and variation over 1–90 days before the collection of each biological sample. An objective model selection procedure was used to determine which hydrochemical determinand, and over what time period, best explained variation in the biological indices.
Stressor‐specific indices derived from macroinvertebrates which purportedly assess stress from low flows, excess fine sediment, nutrient enrichment, pesticides and organic pollution were significantly inter‐correlated and reflected periods of low oxygen concentration, even though only one index (ASPTWHPT, average score per taxon) was designed for this purpose. Changes in community composition resulting from one stressor frequently lead to confounding effects on stressor‐specific indices.
Variation in ASPTWHPT was best described by dissolved oxygen calculated as Q5 over 10 days, suggesting that low oxygen events had most influence over this period. Longer‐term effects were apparent, but were masked by recovery. Macroinvertebrate abundance was best described by Q95 of stream velocity over 60 days, suggesting a slower recovery in numbers than in the community trait reflected by ASPTWHPT.
Although use of ASPTWHPT was supported, we recommend that additional independent evidence should be used to corroborate any conclusions regarding the causes of degradation drawn from the other stressor‐specific indices. The use of such stressor‐specific indices alone risks the mistargeting of management strategies if the putative stressor‐index approach is taken to be more reliable than the results herein suggest.
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