Size-Resolved Fluorescence Underscores Negligible Interaction of Dissolved Organic Matter During Conservative Mixing in a Large Boreal River

Although river mixing occurs widely in nature, the corresponding evolution of dissolved organic matter (DOM) composition remains poorly understood. Here, surface water samples were collected at multiple transects in the lower Athabasca River (LAR) under base-flow conditions. Asymmetric flow field-flow fractionation (AF4) coupled to online excitation-emission measurements (EEMs) and parallel factor analysis (PARAFAC) were utilized to investigate the size distribution of fluorescent DOM components during river mixing and the corresponding variation in size-resolved fluorescence. The majority of fluorescent components occurred at 0.810 and 1.170 kDa, reflecting the small size of the DOM molecules with maximum fluorescence. The loadings of fluorescence normalized to absorbance at 254 nm (A254) were highest for most terrestrial humic-like components, followed by the microbial humic-like component, and the protein-like components. Differences in size-resolved fluorescence were observed between DOM in humic-rich tributaries and in the mainstem of the LAR upstream of tributary inputs. The trend of variations in the A254-normalized PARAFAC loadings of terrestrial humic-like components also illustrates conservative mixing of aromatic-rich terrestrial DOM across size fractions in the LAR. From a molecular point of view, the mixing of fluorescent DOM occurred linearly and simultaneously across sizes without any evidence of aggregation, sedimentation, or changes in the fluorescence or concentration of any size fraction over the >60 km required for complete mixing of the river and its tributaries. Overall, this study provides insights into the size characteristics of fluorescent components of DOM and their conservative mixing behavior in large boreal rivers

The Contribution of Endmembers to Mixtures of Leaf Leachates and Riverine DOM can be Determined by Measuring Their Size and Fluorescence Properties

The molecular mass distribution (MMD) and fluorescence properties of dissolved organic matter (DOM) are important characteristics for tracing and predicting its pathways, processes, and fate in aquatic systems. For the first time, asymmetrical flow field-flow fractionation (AF4) with coupled absorbance and fluorescence detectors was used to determine the contribution of endmembers to three mixtures of leaf leachate and riverine DOM in various proportions. Parallel factor analysis (PARAFAC) and fractogram deconvolution were used to decompose and distinguish the size distributions and fluorescence excitation-emission matrices (EEMs) of mixture constituents. It was determined that: 1) Both size and optical properties were conservative tracers in mixtures; 2) Fractogram deconvolution was extremely helpful for discriminating endmember size properties; 3) The contributions of endmembers to overall DOC concentration were accurately estimated using both the proportion of a humic-like PARAFAC component (0.93 < R2 < 1.00), and the ratios of deconvoluted peaks (0.88 < R2 < 0.98). The fluorescence at the peak maximum of the MMD was lacking in protein-/polyphenol-like and microbial humic-like fluorescence compared to the whole sample (−11 ± 9 and −10 ± 7%, respectively); however, the contribution of endmembers to the MMD (A254) were also effectively predicted using both the proportion of a microbial humic-like PARAFAC component (0.91 < R2 < 0.98) and the ratio of deconvoluted peaks (0.94 < R2 < 0.98)

Metal-free sampling methods for dust, rainwater, surface water, plants, and sediments: A selection of unique tools from the SWAMP laboratory

Contamination control remains one of the greatest challenges for the reliable determination of many trace elements in environmental samples. Here we describe a series of metal-free sampling devices and tools designed and constructed specifically to minimize the risk of contamination by trace elements during sampling of dust, rainwater, surface water, plants, and sediments. Plastic components fabricated using 3-D printing include polylactic acid (PLA), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polypropylene (PP), polycarbonate (PC) and PC with carbon fibre. When additional strength is needed (e.g. supporting structural components), carbon fibre, aluminum (Al), or 316 stainless steel (SS) is used. Other plastics employed include acrylic and vinyl. Epoxy glue or SS may be used for joining components, but do not come into contact with the samples. Ceramic (zirconium dioxide) cutting blades are used where needed. Each plastic material was evaluated for contaminant trace elements by leaching with high purity nitric acid in the metal-free, ultraclean SWAMP laboratory. The devices were tested in the field to evaluate their performance and durability. When combined with appropriate cleaning procedures, the equipment enables ultraclean collection for trace element analysis of environmental media. • Plastic sampling devices were designed and constructed using 3D printing of PLA, PET, PETG or PP. • Leaching characteristics of plastic components were evaluated using high purity nitric acid in a metal-free, ultraclean laboratory. • Each sampling device was successfully field-tested in industrial settings (near open pit bitumen mines and upgraders), and in remote locations of northern Alberta, Canada

Lysimeter Sampling System for Optimal Determination of Trace Elements in Soil Solutions

Understanding trace element (TE) composition and behavior in soil solution is extremely important for assessing ecological and human health impacts. Using lysimeters to collect soil solution with minimum alteration to the in situ phase distribution and concentration of TEs will facilitate a more accurate assessment. However, different lysimeter materials and sampling conditions may lead to vastly different results, demonstrating the need for the optimal choice of lysimeter depending upon environmental conditions. There is no general agreement or overview discussing the best lysimeter type and sampling system to use under various conditions. This review provides a critical summary of various lysimeters that can be used to collect soil solutions for the analysis of TEs and thereby provides key guidance for developing the best lysimeter sampling system for conditions and research questions of interest. This includes a range of aspects related to lysimeters, such as different types and materials, the basic principles of design and operation, advantages and disadvantages, challenges and limitations, techniques for cleaning and pretreatment, correct installation procedures, the influence of soil physical and chemical properties on sampling, and existing research gaps within this field

Size fractionation of dissolved (<0.45 µm) trace elements from extracted soil with water and CaCl2 using AF4-UV-ICPMS to predict their bioavailability

Dissolved (<0.45 µm) trace elements (TEs) represent the sum of free ions, simple complexes and colloid-associated forms which have different mobility and bioavailability in soils. The distribution of TEs amongst these chemical forms was directly quantified in soil extracts using asymmetric flow field-flow fractionation (AF4) coupled to ultraviolet–visible absorbance spectrophotometry (UV) and inductively coupled plasma mass spectrometry (ICP-MS). The soil extracts were obtained using single extraction method with water and 0.01 M CaCl2, respectively. The yields of dissolved TEs extracted from the soils were profoundly impacted by extractants. Using AF4-UV-ICPMS, we show that dissolved species of Ba, Cr, Li, Mn and Mo were primarily present as “truly dissolved”/mainly ionic species (<1 kDa), e.g., hydrated cations, simple complexes or oxyanions, and therefore, likely represented the most bioavailable fraction. The distribution of these TEs amongst dissolved forms was unaffected by the different extractants. However, their dissolved concentrations were profoundly affected. Distributions of Al, As, Co, Cu, Fe, Ni, Pb, Th, Tl, U, V and Zn among the various chemical forms significantly differed with water and CaCl2 extractants. In water extracts, a greater proportion of these elements was associated with colloidal forms having sizes from 1 kDa to 0.45 µm, i.e., dissolved organic matter (DOM) or/and inorganic colloids. Water not only released greater colloid-complexed concentrations of TEs, like Al, As, Fe, Pb, Th, Tl, U and V, but also liberated greater amounts associated with ionic and small forms. Extractants like water and CaCl2 are useful for recovering bioavailable TEs from soils. However, the dissolved TEs extracted using water or CaCl2 represented TE concentrations and forms with different bioavailability. The AF4-UV-ICPMS technique is useful for directly quantifying TEs existing as mainly ionic species and those bound with DOM and inorganic colloids, and thus offers clear insight into their bioavailability in soils. This method also facilitates a better understanding of the effects of extractants on estimating TE bioavailability

AF4-ICPMS with the 300 Da Membrane To Resolve Metal-Bearing “Colloids” < 1 kDa: Optimization, Fractogram Deconvolution, and Advanced Quality Control

The smallest colloids exert a disproportionately large influence on colloidal systems owing to their greater surface area; however, the challenges of working in the smaller size range have limited most field-flow fractionation-ICPMS analyses to sizes > ca. 1 kDa. We discuss considerations and present solutions for overcoming these challenges, including high pressures associated with using the 300-Da membrane, calibration in this small size range, accounting for drifting LODs and separation conditions during membrane aging, and optimizing the compromise between resolution and recovery. Necessary flow program ranges for observing pressure limits are discussed, and calibration is conducted using a combination of bromophenol blue and polystyrene size standards. The impact of membrane drift on size is demonstrated and effectively corrected by routine calibration. Separation conditions are optimized by monitoring the recovery and resolution of several trace metals. A precise, high-resolution separation is achieved using fractogram deconvolution to fully resolve overlapping peaks. Method effectiveness and precision are demonstrated through triplicate analyses of three natural water samples: <i>M</i>_p = 2.89 ± 0.04, 3.20 ± 0.03 and 3.50 ± 0.12 kDa for DOM-associated Fe in the three samples (±95% CI). A primarily inorganic Fe fraction with <i>M</i>_p = 14.7 ± 0.5 kDa was also resolved from the DOM-associated fraction. Quality control methods and considerations for optimizing flow conditions are detailed in the Supporting Information as a guide for researchers seeking to analyze colloids in this smallest size range using AF4-ICPMS with the 300-Da membrane

AF4-ICPMS with the 300 Da Membrane To Resolve Metal-Bearing “Colloids” < 1 kDa: Optimization, Fractogram Deconvolution, and Advanced Quality Control

The smallest colloids exert a disproportionately large influence on colloidal systems owing to their greater surface area; however, the challenges of working in the smaller size range have limited most field-flow fractionation-ICPMS analyses to sizes > ca. 1 kDa. We discuss considerations and present solutions for overcoming these challenges, including high pressures associated with using the 300-Da membrane, calibration in this small size range, accounting for drifting LODs and separation conditions during membrane aging, and optimizing the compromise between resolution and recovery. Necessary flow program ranges for observing pressure limits are discussed, and calibration is conducted using a combination of bromophenol blue and polystyrene size standards. The impact of membrane drift on size is demonstrated and effectively corrected by routine calibration. Separation conditions are optimized by monitoring the recovery and resolution of several trace metals. A precise, high-resolution separation is achieved using fractogram deconvolution to fully resolve overlapping peaks. Method effectiveness and precision are demonstrated through triplicate analyses of three natural water samples: <i>M</i>_p = 2.89 ± 0.04, 3.20 ± 0.03 and 3.50 ± 0.12 kDa for DOM-associated Fe in the three samples (±95% CI). A primarily inorganic Fe fraction with <i>M</i>_p = 14.7 ± 0.5 kDa was also resolved from the DOM-associated fraction. Quality control methods and considerations for optimizing flow conditions are detailed in the Supporting Information as a guide for researchers seeking to analyze colloids in this smallest size range using AF4-ICPMS with the 300-Da membrane

Geochemical and biological controls on the ecological relevance of total, dissolved and colloidal forms of trace elements in large boreal rivers: review and case studies

The concentrations of trace elements (TEs) in large boreal rivers can fluctuate markedly due to changing water levels and flow rates associated with spring melt and variable contributions from tributaries and groundwaters, themselves having different compositions. These fluctuating and frequently high concentrations create regulatory challenges for protecting aquatic life. For example, water quality criteria do not account for changes in flow regimes that can result in TE levels that may exceed regulatory limits, and neither do they account for the markedly different lability and bioaccessibility of suspended solids. This review addresses the geochemical and biological processes that govern the lability and bioaccessibility of TEs in boreal rivers, with an emphasis on the challenges posed by the colloidal behaviour of many TEs, and their relationship to the dissolved fraction (i.e., <0.45 μm in size). After reviewing the processes and dynamics that give rise to the forms and behaviour of TEs in large boreal rivers, their relevance for aquatic organisms and the associated relationships between size and lability and bioaccessibility are discussed. The importance of biological variables and different forms of TEs for limiting lability and bioaccessibility are also addressed. Two case studies emphasize seasonal fluctuations and accompanying changes in the distribution of TE amongst different size fractions and associated colloidal species in large boreal rivers: the Northern Dvina and one of its tributaries, the Pinega River, both in Russia, and the Athabasca River in Alberta, Canada. Water quality in the Athabasca River is briefly discussed with respect to Canadian guidelines.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author