Search

High concentrations of arsenic (As) in groundwater threaten the environment and public health. Geogenically, groundwater As contamination predominantly occurs via its mobilization from underground As-rich sediments. In an aquatic ecosystem, As is typically driven by several underlying processes, such as redox transitions, microbially driven reduction of iron (Fe) oxide minerals, and release of associated As. Notably, dissolved As mobilized from soils and sediments exhibits high affinity for dissolved organic matter (DOM). Thus, high DOM concentrations can increase As mobility. Therefore, it is crucial to understand the complex interactions and biogeochemical cycling of As, DOM, and Fe oxides. This review collates knowledge regarding the fate of As in multicomponent As-DOM-Fe systems, including ternary complexes involving both Fe and DOM. Additionally, the release mechanisms of As from sediments into groundwater in the presence of both Fe and DOM have been discussed. The mechanisms of As mobilization/sorption at the solid-water interface can be affected by negatively charged DOM competing for sorption sites with As on Fe (oxy)(hydr)oxides and may be further modified by other anionic ubiquitous species such as phosphate, silicic acid, or sulfur. This review emphasizes the need for a comprehensive understanding of the impact of DOM, Fe oxides, and related biogeochemical processes on As mobilization to aquifers. The review identifies important knowledge gaps that may aid in developing applicable practices for preventing the spread of As contamination in aquatic resources and traditional soil management practices., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In most natural groundwaters, sulfide concentrations are low, and little attention has been paid to potential occurrence of thioarsenates (As V S n -II O 4- n 3- with n = 1-4). Thioarsenate occurrence in groundwater could be critical with regard to the efficiency of iron (Fe)-based treatment technologies because previous studies reported less sorption of thioarsenates to preformed Fe-minerals compared to arsenite and arsenate. We analyzed 273 groundwater samples taken from different wells in Bangladesh over 1 year and detected monothioarsenate (MTA), likely formed via solid-phase zero-valent sulfur, in almost 50% of all samples. Concentrations ranged up to >30 μg L -1 (21% of total As). MTA removal by locally used technologies in which zero-valent or ferrous Fe is oxidized by aeration and As sorbs or coprecipitates with the forming Fe(III)hydroxides was indeed lower than for arsenate. The presence of phosphate required up to three times as much Fe(II) for comparable MTA removal. However, in contrast to previous sorption studies on preformed Fe minerals, MTA removal, even in the presence of phosphate, was still higher than that of arsenite. The more efficient MTA removal is likely caused by a combination of coprecipitation and adsorption rendering the tested Fe-based treatment technologies suitable for As removal also in the presence of MTA.

Wetlands fed by rivers can be a sink for elements depending on elemental concentrations, wetland hydrology, geochemistry, vegetation and climate. In the case of the Okavango Delta, northern Botswana, the outflow discharge is a small fraction (2-5%) of the inflow. This has strong potential consequences for the Delta, as it strongly affects element cycling and storage within the Delta. We estimated the inputs, behaviour and distribution of multiple elements along a longitudinal transect within the Okavango Delta, to show potential effects of retention mechanisms of different elements. High annual element input is rather attributed to discharge than to the concentration within the water, which is generally extremely low. We observed minimal enrichment of the elements within the water pathway along the transect from inflow to outlets, implying that element output is negligible. For most elements, we observed a high correlation between storage and sediment organic matter content. The organic matter content within the sediments was higher in the vegetated sediments than in non-vegetated sediments (factor ∼ 10), and a similar trend was found for most elements. In conclusion, organic matter dominated in sediments from vegetated plots and thus plays an important role in retaining the elements within the sediments of the Delta. This finding has major implications for e.g. planning constructed wetlands for water purification or element retention especially in areas with high evapotranspiration.

The invertebrate shredder Gammarus pulex L. is a key species for aquatic carbon turnover via litter decomposition and can thrive in high-arsenic (As) environments. To understand their strategies for coping with increased As concentrations while fulfilling their ecosystem functions, we analyzed the As concentration and speciation in their aquatic habitat and in leaves with heterotrophic biofilms as their natural food source. We also followed the As distribution and speciation on the cuticle and within the body of G. pulex by X-ray absorption spectroscopic imaging. Half of the total As on G. pulex was found to be associated with the cuticle but was not taken up. Removing this externally bound As yielded only arsenate in the wash solution which reflects the speciation of the surrounding aquatic phase and shows that this As does not undergo any biotransformation. The major pathway into the organism is suggested to be incorporation via food intake, but only very low amounts of As were taken up or translocated from the gut system to other tissues. In one of the main food sources, leaves, 68% arsenate and 29% monomethylarsenate were found. After ingestion into the gut system, up to 23% of the more toxic arsenite was seen, but a substantial share was methylated to dimethylarsenate (46-56%). Little arsenate and arsenite were found in the adjacent tissues. Besides 76-80% mono- and di-methylarsenate, 10-21% of the As was complexed as As(III)-S species. G. pulex plays an important role in As cycling and our results indicate that As translocation from the gut to other tissues is minimized, but a transformation to other As-species occurred., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The increasing cultivation of genetically modified corn plants (Zea mays) during the last decades is suggested as a potential risk to the environment. One of these genetically modified variety expressed the insecticidal Cry1Ab protein originating from Bacillus thuringiensis (Bt), resulting in resistance against Ostrinia nubilalis, the European corn borer. Transgenic litter material is extensively studied regarding the decomposition in soils. However, only a few field studies analyzed the fate of the Cry1Ab protein and the impact of green and senescent leaf litter from corn on the decomposition rate and related ecosystem functions in aquatic environments. Consequently, a microbial litter decomposition experiment was conducted under controlled semi-natural conditions in batch culture using two maize varieties: one variety with Cry1Ab and another one with the appertaining Iso-line as control treatment. The results showed no significant differences between the treatment with Cry1Ab and the Iso-line regarding loss of total mass in dry weight of 43% for Iso-line and 45% for Bt-corn litter, lignin content increased to 137.5% (Iso-line) and 115.7% (Bt-corn), and phenol loss decreased by 53.6% (Iso-line), 62.2% (Bt-corn) during three weeks of the experiment. At the end of the experiment Cry1Ab protein was still detected with 6% of the initial concentration. A slightly but significant lower cellulose content was found for the Cry1Ab treatment compared to the Iso-line litter at the end of the experiment. The significant higher total protein (25%) and nitrogen (25%) content in Bt corn, most likely due to the additionally expression of the transgenic protein, may increase the microbial cellulose degradation and decrease microbial lignin degradation. In conclusion a relevant year by year input of protein and therefore nitrogen rich Bt corn litter into aquatic environments may affect the balanced nutrient turnover in aquatic ecosystems., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Plant litter and organic sediments are main sinks for metals and metalloids in aquatic ecosystems. The effect of invertebrates as key species in aquatic litter decomposition on metal/metalloid fixation by organic matter is described only for shredders, but for grazers as another important animal group less is known. Consequently, a laboratory batch experiment was conducted to examine the effect of invertebrate grazers (Lymnaea stagnalis L.) on metal/metalloid fixation/remobilization during aquatic litter decomposition. It could be shown that invertebrate grazers facilitate significantly the formation of smaller sizes of particulate organic matter (POM), as shown previously for invertebrate shredders. The metal/metalloid binding capacity of these smaller particles of POM is higher compared to leaf litter residuals. But element enrichment is not as high as shown previously for the effect by invertebrate shredders. Invertebrate grazers enhance also the mobilization of selected elements to the water, in the range also proven for invertebrate shredders but different for the different elements. Nonetheless invertebrate grazers activity during aquatic litter decomposition leads to a metal/metalloid fixation into leaf litter as part of sediment organic matter. Hence, the effect of invertebrate grazers on metal/metalloid fixation/remobilization contrasts partly with former assessments revealing the possibility of an enhanced metal/metalloid fixation., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Aquatic sediments represent a possibly significant sink of soluble inorganic elements/pollutants (metals, metalloids and rare earth elements) in ecosystems. Bioturbation/bioirrigation was shown to affect the remobilization of some elements where others seem to be unaffected. In view of these contrasting results, the effect of bioturbation/bioirrigation was examined using the invertebrate Chironomus plumosus in a laboratory experiment for a broad range (18) of elements. The experiments revealed an impact of invertebrate bioturbation/bioirrigation on elemental remobilization depending on chemical characteristics of the element ranging from strong influence to influence only at start when the larvae dig into the sediments. Three different types of remobilization were found: (i) element mobilization highly influenced by bioturbation/bioirrigation (DOC, N, Mg, Ca, Sr, Mo and U), (ii) strong element mobilization by bioturbation/bioirrigation at the start of the experiment when the larvae dig into the sediments and afterwards strong decrease, but to higher levels compared to values of treatments without invertebrate impact (Mn, Ni, As, Cd and Cs), and (iii) strong element mobilization by bioturbation/bioirrigation at start when the larvae dig into the sediments and afterwards strong decrease to levels found in treatments without invertebrate impact (Al, Fe, Co, Cu, Zn and Ce). During the experiment a distinct accumulation of most of the elements in C. plumosus was found, where they were not so much bound to the outer surface of C. plumosus but more within the gut system including food and feces. Hence, bioturbation/bioirrigation is certainly a main process controlling mobilization of elements from sediments., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Metal and metalloid mobilization processes within seepage water are of major concern in a range of water reservoir systems. The mobilization process of arsenic and heavy metals within a dam and sediments of a drinking water reservoir was investigated. Principle component analysis (PCA) on time series data of seepage water showed a clear positive correlation of arsenic with iron and DOC (dissolved organic carbon), and a negative correlation with nitrate due to respiratory processes. A relationship of reductive metal and metalloid mobilization with respiration of old carbon was shown. The system is influenced by sediment layers as well as a recent DOC input from degraded ombrotrophic peatbogs in the catchment area. The isotopic composition ((12)C, (13)C and (14)C) of DOC is altered along the path from basin to seepage water, but no significant changes in structural parameters (LC-OCD-OND, FT-IR) could be seen. DIC (dissolved inorganic carbon) in seepage water partly originates from respiratory processes, and a higher relationship of it with sediment carbon than with the DOC inventory of infiltrating water was found. This study revealed the interaction of respiratory processes with metal and metalloid mobilization in sediment water flows. In contrast to the presumption that emerging DOC via respiratory processes mainly controls arsenic and metal mobilization it could be shown that the presence of aged carbon compounds is essential. The findings emphasize the importance of aged organic carbon for DOC, DIC, arsenic and metal turnover.

Increasing arsenic concentrations in freshwater ecosystems is of global concern. Processes affecting arsenic fluxes in catchments are known. These processes are in turn controlled by the underlying geology and air pollution history. In contrast to the knowledge on catchment processes less is known about the hydrochemical processes controlling the fixation/remobilization of arsenic within lakes and artificial reservoirs. Consequently, we examined a reservoir system in the Ore Mts. (Germany) regarding its sink and source potentials affecting arsenic fluxes. This area was faced with heavy deposition inputs from coal burning based acid rain until the beginning of the 1990s. Hereafter concentrations of sulfate and nitrate in runoff waters decreased, whereas dissolved organic carbon (DOC) concentrations are still increasing. Along with this, arsenic concentrations in the water discharge from the catchments increase. Our results reveal that the sediments of the investigated reservoir system contain high inventories of arsenic in association with ferric and organic phases. A nitrate deficit dependent arsenic release is suggested. It is indicated that arsenic release from the reservoir sediments may be controlled by water nitrate concentration, which in turn is dependent on the nitrate concentration in the runoff water from the catchment., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Plant litter and organic sediments are a main sink for metals and metalloids in aquatic ecosystems. The effect of invertebrate shredder (a key species in litter decay) on metal/metalloid fixation by organic matter is described only under alkaline water conditions whereas for slightly acidic waters nothing can be found. Furthermore, less is known about the effect of invertebrate shredders on the quality of dissolved organic carbon (DOC) and nitrogen (DON) released during litter decay. We conducted an experiment to investigate the impact of invertebrate shredder (Gammarus pulex) on metal/metalloid fixation/remobilization and on the quality of DOC/DON released under slightly acidic water conditions. During decomposition of leaf litter, invertebrate shredder facilitated significantly the emergence of smaller particle sizes of organic matter. The capacity of metal fixation was significantly higher in smaller particles (POM 2,000-63 μm) compared to original leaf litter and litter residues. Thus, G. pulex enhanced metal fixation by organic partition of sediments by increasing the amount of smaller particle of organic matter in aquatic ecosystems. In contrast, the capacity of metal/metalloid fixation in the smallest fraction of POM (<63 μm) was lower compared with leaf residues in treatment without invertebrates. Remobilization of metals and metalloids was very low for all measured elements. A significant effect of invertebrates on quantitative formation of DOC/DON was confirmed. The quality of released DOC/DON, which may affect metal/metalloid remobilization, was also significantly affected by invertebrate shredders (e.g., more carboxylates). Hence, invertebrate shredder enhanced significantly the fixation of metals/metalloids into POM in slightly acidic environments.

The focus of this article is to combine two main areas of research activities in freshwater ecosystems: the effect of inorganic pollutants on freshwater ecosystems and litter decomposition as a fundamental ecological process in streams. The decomposition of plant litter in aquatic systems as a main energy source in running water ecosystems proceeds in three distinct temporal stages of leaching, conditioning and fragmentation. During these stages metals and metalloids may be fixed by litter, its decay products and the associated organisms. The global-scale problem of contaminated freshwater ecosystems by metals and metalloids has led to many investigations on the acute and chronic toxicity of these elements to plants and animals as well as the impact on animal activity under laboratory conditions. Where sorption properties and accumulation/remobilization potential of metals in sediments and attached microorganisms are quite well understood, the combination of both research areas concerning the impact of higher trophic levels on the modification of sediment sorption conditions and the influence of metal/metalloid pollution on decomposition of plant litter mediated by decomposer community, as well as the effect of high metal load during litter decay on organism health under field conditions, has still to be elucidated. So far it was found that microbes and invertebrate shredder (species of the genera Gammarus and Asellus) have a significant influence on metal fixation on litter. Not many studies focus on the impact of other functional groups affecting litter decay (e.g. grazer and collectors) or other main processes in freshwater ecosystems like bioturbation (e.g. Tubifex, Chironomus) on metal fixation/release., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Organic-rich sediments are known to be effective accumulators for uranium and arsenic. Much is known about the capacity for metal or metalloid fixation by microbes and organic compounds as well as inorganic sediment particles. Experiments investigating the effect of microbes on the process of metal fixation in sediments require sterilized sediments as control treatment which is often realized by gamma-sterilization. Only few studies show that gamma-sterilization has an effect on the remobilization of metal and metalloids and on their physico-chemical properties. These studies deal with sediments with negligible organic content whereas almost nothing is known about organic-rich sediments including a probably high microbial activity. In view of this, we investigated the effect of gamma-sterilization of organic-rich sediments on uranium and arsenic fixation and release. After ten days within an exposure experiment we found a significant higher remobilization of uranium and arsenic in sterile compared to unsterile treatments. In line with these findings the content of dissolved organic carbon (DOC), manganese, and iron increased to even significantly higher concentration in the sterile compared to unsterile treatment. Gamma-sterilization seems to change the physico-chemical properties of organic-rich sediments. Microbial activity is effectively eliminated. From increased DOC concentrations in overlaying water it is concluded that microbes are eventually killed with leaching of cellular compounds in the overlaying water. This decreases the adsorption capacity of the sediment and leads to enhanced uranium and arsenic remobilization., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Invertebrate shredders such as Gammarus pulex are key species in contaminated stream ecosystems. Although a number of previous studies examining differences in metal accumulation between the gut system and remaining tissues of invertebrates exist, few focus on wide range of metals and metalloids that are relevant to contaminated systems. This study compared accumulation of the commonest (at study site) 15 metals and metalloids between the gut system including feces and remaining tissues of G. pulex. All metals and metalloids measured were significantly higher (p<0.001, except Cu p<0.005) in the gut system including feces than remaining tissues of G. pulex. Metals and metalloids in body tissues without the gut system including feces were significantly lower (Al, Cr, Fe and Mn (p<0.005), Sr and U (p<0.01), Co (p<0.05)) in content for a number of elements when compared to washed, whole G. pulex specimens. As well, all elements measured were significantly higher (all elements (p<0.005) except Cu and Co (p<0.05)) in gut system including feces than washed, whole G. pulex specimens. These results indicate that in G. pulex the uptake of all 15 metals and metalloids examined across the gut epithelium is minimalized or that sequestration of these elements in gut epithelial cells may occur., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Organic sediments are known to be a significant sink of inorganic elements in polluted freshwater ecosystems. Hence, we investigated the role of invertebrate shredders (the freshwater shrimp Gammarus pulex L.) in metal and arsenic enrichment into organic partitions of sediments in a wetland stream at former uranium mining site. Metal and metalloid content in leaf litter increased significantly during decomposition, while at the same time the carbon content decreased. During decomposition, G. pulex as a ecosystem engineer facilitated significantly the enrichment of magnesium (250%), manganese (560%), cobalt (310%), copper (200%), zinc (43%), arsenic (670%), cadmium (100%) and lead (1340%) into small particle sizes. The enrichments occur under very high concentrations of dissolved organic carbon. Small particles have high surface area that results in high biofilm development. Further, the highest amounts of elements were observed in biofilms. Therefore, invertebrate shredder like G. pulex can enhance retention of large amounts of metal and arsenic in wetlands., (2010 Elsevier Ltd. All rights reserved.)

In contrast to the classification of most invertebrate shredders being sensitive to uranium, a G. pulex L. population with reproduction was found in a stream at a former uranium mining site with uranium concentrations of 150 microg l(-1) in water and up to 2000 mg kg(-1) DW(-1) (dry weight) in litter born organic sediments. The survival of G. pulex, collected from a site without uranium contamination, was tested in a laboratory microcosm experiment using synthetic uranium-contaminated water and uranium-contaminated but nutrient rich food, simulating physicochemical conditions of water from former uranium mining sites. The results reveal that there are no significant differences in survival rate between individuals exposed and those not exposed to uranium. The uptake of uranium by G. pulex in environments with concentrations in food of 1152 mg kg(-1) in DM (dry mass, organically bound) and in water of 63.9 microg L(-1) is very low (4.48(1.93-8.46) mg kg(-1) in DM). The accumulation of uranium in these invertebrates was verified to be via two pathways: body surface and food. A relevant amount of uranium adsorbs to the body surface where it can readily be desorbed.