This study explores interactions between As and Fe(III) minerals, predominantly schwertmannite and jarosite, in acid mine drainage (AMD) via observations at a former mine site combined with mineral formation and transformation experiments. Our objectives were to examine the effect of As on Fe(III) mineralogy in strongly acidic AMD while also considering associated controls on As mobility. AMD at the former mine site was strongly acidic (pH 2.4 to 2.8), with total aqueous Fe and As decreasing down the flow-path from ∼400 to ∼20 mg L^–1 and ∼33,000 to ∼150 μg L^–1, respectively. This trend was interrupted by a sharp rise in aqueous As(III) and Fe(II) caused by reductive dissolution of As-bearing Fe(III) phases in a sediment retention pond. Attenuation of Fe and As mobility occurred via formation of As(V)-rich schwertmannite, As(V)-rich jarosite, and amorphous ferric arsenate (AFA), resulting in solid-phase As concentrations spanning ∼13 to ∼208 g kg^–1. Schwertmannite and jarosite retained As(V) predominantly by structural incorporation involving AsO₄-for-SO₄ substitution at up to ∼40 and ∼22 mol %, respectively. Arsenic strongly influenced Fe(III) mineral formation, with high As(V) concentrations causing formation of AFA over schwertmannite. Arsenic also strongly influenced Fe(III) mineral evolution over time. In particular, increasing levels of As(V) incorporation within schwertmannite were shown, for the first time, to enhance the transformation of schwertmannite to jarosite. This significant discovery necessitates a re-evaluation of the prevailing paradigm that As(V) retards schwertmannite transformation.

Coastal freshwater wetland chemistry is rapidly changing due to increased frequency of salt water incursion, a consequence of global change. Seasonal salt water incursion introduces sulfate, which microbially reduces to sulfide. Sulfide binds with reduced iron, producing iron sulfide (FeS), recognizable in wetland soils by its characteristic black color. The objective of this study is to document iron and sulfate reduction rates, as well as product formation (acid volatile sulfide (AVS) and chromium reducible sulfide (CRS)) in a coastal freshwater wetland undergoing seasonal salt water incursion. Understanding iron and sulfur cycling, as well as their reduction products, allows us to calculate the degree of sulfidization (DOS), from which we can estimate how long soil iron will buffer against chemical effects of sea level rise. We show that soil chloride, a direct indicator of the degree of incursion, best predicted iron and sulfate reduction rates. Correlations between soil chloride and iron or sulfur reduction rates were strongest in the surface layer (0–3 cm), indicative of surface water incursion, rather than groundwater intrusion at our site. The interaction between soil moisture and extractable chloride was significantly related to increased AVS, whereas increased soil chloride was a stronger predictor of CRS. The current DOS in this coastal plains wetland is very low, resulting from high soil iron content and relatively small degree of salt water incursion. However, with time and continuous salt water exposure, iron will bind with incoming sulfur, creating FeS complexes, and DOS will increase.