5.10 - Dissolved Organic Matter in Freshwaters

Metals are naturally present in freshwater ecosystems but anthropogenic activities like mining operations represent a long-standing concern. Metals released into aquatic environments may affect microbial communities such as periphytic biofilm, which plays a key role as a primary producer in stream ecosystems. Using two 28-day microcosm studies involving two different photoperiods (light/dark cycle of 16/8 vs 8/16), the present study assessed the effects of four increasing nickel (Ni) concentrations (0–6 μM) on two natural biofilm communities collected at different seasons (summer and winter). The two communities were characterized by different structural profiles and showed significant differences in Ni accumulated content for each treatment. For instance, the biofilm metal content was four times higher in the case of summer biofilm at the highest Ni treatment and after 28 days of exposure. Biomarkers examined targeted both heterotrophic and autotrophic organisms. For heterotrophs, the β-glucosidase and β-glucosaminidase showed no marked effects of Ni exposure and were globally similar between the two communities suggesting low toxicity. However, the photosynthetic yield confirmed the toxicity of Ni on autotrophs with maximum inhibition of 81 ± 7% and 60 ± 1% respectively for the summer and winter biofilms. Furthermore, biofilms previously exposed to the highest long-term Ni concentration ([Ni²⁺] = 6 μM) revealed no acute effects in subsequent toxicity based on the PSII yield, suggesting a tolerance acquisition by the phototrophic community. Taken together, the results suggest that the biofilm response to Ni exposure was dependent of the function considered and that descriptors such as biofilm metal content could be seasonally dependent, information of great importance in a context of biomonitoring.

This paper aims to critically review the importance of geochemical fingerprinting and tracing using biomarkers and stable isotopes in the riverine ecosystem and depicts that isotopic ratios of δ¹³C, δ¹⁵N, and δ³⁴S can be used for tracing pollution sources. Stable isotopes like carbon, hydrogen, nitrogen, oxygen, and sulfur are being used for this purpose, and their isotopic signatures are primarily used to distinguish close sources of organic matter through dual isotopes. The present review is articulated to bridge the critical research gaps of the previous and contemporary documented literature on the genesis and transport of OM between freshwater and marine systems. This review comprehensively provides methods and techniques in geochemical tracing and discusses the future directions to address the challenges of the current methods to enhance the knowledge about the source identification of organic matter in the riverine environment. Tracer geochemistry emphasizes the implications of elemental abundances and isotope ratio variations in geologic substances to track natural earth processes, anthropogenic contaminants, and geochemical signatures in the hydrologic system. The principal constituent of organic matter comprises humic substances like humic acid, fulvic acid, and humin, and these comprise 50–75% of the sediments and DOC in natural waters. Their structural and functional characterization is required to elucidate the transport and fate of organic matter, which are often influenced by several paleoenvironmental factors.

The Arctic faces many environmental challenges, including the continued exploitation of its mineral resources such as nickel (Ni). The responsible development of Ni mining in the Arctic requires establishing a risk assessment framework that accounts for the specificities of this unique region. We set out to conduct preliminary assessments of Ni exposure and effects in aquatic Arctic ecosystems. Our analysis of Ni source and transport processes in the Arctic suggests that fresh, estuarine, coastal, and marine waters are potential Ni-receiving environments, with both pelagic and benthic communities being at risk of exposure. Environmental concentrations of Ni show that sites with elevated Ni concentrations are located near Ni mining operations in freshwater environments, but there is a lack of data for coastal and estuarine environments near such operations. Nickel bioavailability in Arctic freshwaters seems to be mainly driven by dissolved organic carbon (DOC) concentrations with bioavailability being the highest in the High Arctic, where DOC levels are the lowest. However, this assessment is based on bioavailability models developed from non-Arctic species. At present, the lack of chronic Ni toxicity data on Arctic species constitutes the greatest hurdle toward the development of Ni quality standards in this region. Although there are some indications that polar organisms may not be more sensitive to contaminants than non-Arctic species, biological adaptations necessary for life in polar environments may have led to differences in species sensitivities, and this must be addressed in risk assessment frameworks. Finally, Ni polar risk assessment is further complicated by climate change, which affects the Arctic at a faster rate than the rest of the world. Herein we discuss the source, fate, and toxicity of Ni in Arctic aquatic environments, and discuss how climate change effects (e.g., permafrost thawing, increased precipitation, and warming) will influence risk assessments of Ni in the Arctic.

Biofilms play a key role in aquatic ecosystems. They are ubiquitous, even in the most contaminated ecosystems, and have great potential as biomonitors of exposure to contaminants such as metals. Freshwater biofilms and surface waters were sampled in two active mining areas of Canada: in the northern part of Nunavik (Quebec) and in the Greater Sudbury area (Ontario). Significant linear relationships were found between both total dissolved and free metal ion concentrations with biofilm metal contents for Cu and Ni, but not for Cd. When pH was below 6, biofilms accumulated less metals than at higher pHs. These results confirm that protons have a protective effect, leading to lower internalized metal concentrations. When considering only the sites where pH was above 6, the linear relationships between metal concentrations in water and in biofilms were improved for all three studied metals. The presence of metal ions could also modify the internalization of a given metal. To further study the role of cations as competitors to Cu, Ni and Cd uptake, relationships between the ratio of biofilm metal contents (Cu, Ni and Cd) on the ambient free metal ion concentrations were built as a function of potential cation competitors, such as major cations and metals. Surprisingly, our data suggest that calcium plays a minor role in preventing metal accumulation as compared to magnesium and possibly other metals. At a global scale, metal accumulation remained highly consistent between the two studied regions and over the sampling period, despite differences in ambient physicochemical water characteristics, climate or types of ecosystems. Metal bioaccumulation is thus a promising biomarker to assess metal bioavailability in a mining context. Nevertheless, more data are still required to further highlight the contribution of each competitor in metal accumulation by biofilms and to be able to build a unifying predictive model.

Chromophoric dissolved organic matter (CDOM) plays an important role in the biogeochemical cycle and energy flow of aquatic ecosystems. Thus, systematic and comprehensive understanding of CDOM dynamics is critically important for aquatic ecosystem management. CDOM spans multiple study fields, including analytical chemistry, biogeochemistry, water color remote sensing, and global environmental change. Here, we thoroughly summarize the progresses of recent studies focusing on the characterization, distribution, sources, composition, and fate of CDOM in inland waters. Characterization methods, remote sensing estimation, and biogeochemistry cycle processes were the hotspots of CDOM studies. Specifically, optical, isotope, and mass spectrometric techniques have been widely used to characterize CDOM abundance, composition, and sources. Remote sensing is an effective tool to map CDOM distribution with high temporal and spatial resolutions. CDOM dynamics are mainly determined by watershed-related processes, including rainfall discharge, groundwater, wastewater discharges/effluents, and biogeochemical cycling occurring in soil and water bodies. We highlight the underlying mechanisms of the photochemical degradation and microbial decomposition of CDOM, and emphasize that photochemical and microbial processes of CDOM in inland waters accelerate nutrient cycling and regeneration in the water column and also exacerbate global warming by releasing greenhouse gases. Future study directions to improve the understanding of CDOM dynamics in inland waters are proposed. This review provides an interdisciplinary view and new insights on CDOM dynamics in inland waters.

In this study, surface water samples were collected at sites located in the lowest reaches of closed (Geum) (i.e. with an estuary dam at the river mouth) and open (Seomjin) estuary systems between May 2016 and May 2018. We analyzed concentrations and stable isotopes of particulate organic carbon (POC) and dissolved organic carbon (DOC) to assess OC sources, to estimate fluxes of riverine OC, and to assess some of the factors driving OC exports in these two contrasting Korean estuary systems. Our geochemical results suggest that the contribution of the phytoplankton-derived POC to the total POC pool was larger in the Geum River than in the Seomjin River. Notably, a heavy riverine algae bloom occurred in the Geum River in August 2016, resulting in a high carbon isotopic composition (−19.4‰) together with low POC/PN ratio (<10) and POC/Chl-a ratio (<100). In contrast, potential DOC sources in both the Geum River and the Seomjin River were a mixture of C₃-derived forest soils and cropland organic matter. During the study period, the catchment area-normalized fluxes of POC and DOC were 0.40 × 10⁻³ tC/km²/yr and 6.5 × 10⁻² tC/km²/yr in the Geum River and 5.2 × 10⁻⁴ tC/km²/yr and 8.6 × 10⁻⁴ tC/km²/yr in the Seomjin River, respectively. It appears that the POC flux was more weakly associated with the water discharge in the Geum River than in the Seomjin River, but the DOC fluxes were in general controlled by the water discharges in both rivers. Accordingly, the estuary dam of the Geum River might be one of the most strongly influencing factors on seasonal patterns in POC fluxes into the adjacent coastal seas, strongly modifying water residence times and thus biogeochemical processes.