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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 flooded paddy soils, inorganic and methylated thioarsenates contribute substantially to arsenic speciation besides the much-better-investigated oxyarsenic species, and thioarsenate uptake into rice plants has recently been shown. To better understand their fate when soil redox conditions change, that is, from flooding to drainage to reflooding, batch incubations and unplanted microcosm experiments were conducted with two paddy soils covering redox potentials from E H -260 to +200 mV. Further, occurrence of thioarsenates in the oxygenated rice rhizosphere was investigated using planted rhizobox experiments. Soil flooding resulted in rapid formation of inorganic thioarsenates with a dominance of trithioarsenate. Maximum thiolation of inorganic oxyarsenic species was 57% at E H -100 mV. Among all thioarsenates, dimethylated monothioarsenate showed the least transformation upon prolonged oxidation. It also was the major thiolated arsenic species in the rhizosphere with concentrations comparable to its precursor dimethylated oxyarsenate, which is especially critical since dimethylated monothioarsenate is highly carcinogenic.E H 0 mV. Dithiolated species dominated over monothiolated species below E H -100 mV. Among all thioarsenates, dimethylated monothioarsenate showed the least transformation upon prolonged oxidation. It also was the major thiolated arsenic species in the rhizosphere with concentrations comparable to its precursor dimethylated oxyarsenate, which is especially critical since dimethylated monothioarsenate is highly carcinogenic.

Rice straw increasingly remains on the fields for nutrient supply to the next generation of crop plants. It can be applied either fresh or after burning to black carbon or ash. A central concern during rice cultivation is accumulation of carcinogenic arsenic and the question arises how much rice straw application contributes to nutrient versus arsenic supply in paddy fields. Laboratory incubation experiments were performed to assess the effect of rice straw, black carbon and ash on element mobilization. Our experiments showed initially higher silicon and phosphorus release from black carbon compared to fresh straw amendments. However, more re-sorption to soil lead to finally slightly lower pore water concentrations for black carbon versus fresh straw amendments. Highest arsenic, iron, manganese and dissolved organic carbon concentrations were observed after fresh rice straw application. Black carbon and ash application lead to only minor increases of arsenic compared to controls without amendments. Overall, for silicon and phosphorus the soil acts as sink while for iron and arsenic it was the main source. In summary, burning of rice straw to black carbon prior to application seems to yield a high increase in desired nutrient and a decrease in undesired arsenic mobilization in paddy soils.

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.

Organic sediments in aquatic ecosystems are well known sinks for nutrients, silicon, and metal(loid)s. Organic matter-consuming organisms like invertebrate shredders, grazers, and bioturbators significantly affect element fixation or remobilization by changing redox conditions or binding properties of organic sediments. Little is known about the effect of filter feeders, like the zebra mussel Dreissena polymorpha, an invasive organism in North American and European freshwater ecosystems. A laboratory batch experiment exposing D. polymorpha (∼1200 organisms per m 2 ) to organic sediment from a site contaminated with arsenic, copper, lead, and uranium revealed a significant uptake and accumulation of arsenic, copper, iron, and especially uranium both into the soft body tissues and the seashell. This is in line with previous observations of metal(loid) accumulation from biomonitoring studies. Regarding its environmental impact, D. polymorpha significantly contributed to mobilization of silicon, iron, phosphorus, arsenic, and copper and to immobilization of uranium (p < 0.001), probably driven by redox conditions, microbial activity within the gut system, or active control of element homeostasis. No net mobilization or immobilization was observed for zinc and lead, because of their low mobility at the prevailing pH of 7.5-8.5. The present results suggest that D. polymorpha can both ameliorate (nutrient mobilization, immobilization of toxicants mobile under oxic conditions) or aggravate negative effects (mobilization of toxicants mobile under reducing conditions) in ecosystems. Relating the results of the present study to observed population densities in natural freshwater ecosystems suggests a significant influence of D. polymorpha on element cycling and needs to be considered in future studies., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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.)

Elevated arsenic content in food crops pose a serious human health risk. Apart from rice wheat being another main food crop is possibly cultivated on contaminated sites. But for wheat uptake mechanisms are not entirely understood especially with regard to nutrient fertilization and different moisture regimes taking into account heavy rainfall events due to climate change. Here we show that especially higher P-fertilization under changing redox conditions may enhance arsenic uptake. This counteracts with higher N-fertilization reducing arsenic transfer and translocation into aboveground plant parts for both higher P-fertilization and reducing soil conditions. Arsenic speciation did not change in grain but for leaves P-fertilization together with reducing conditions increased the As(V) content compared to other arsenic species. Our results indicate important dependencies of nutrient fertilization, moisture conditions and substrate type on As accumulation of wheat as one of the most important crop plants worldwide with implications for agricultural practices.

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.)

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.)

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.)

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. [ABSTRACT FROM AUTHOR]