Soil phosphorus cycling across a 100-year deforestation chronosequence in the Amazon rainforest.

Deforestation of tropical rainforests is a major land use change that alters terrestrial biogeochemical cycling at local to global scales. Deforestation and subsequent reforestation are likely to impact soil phosphorus (P) cycling, which in P-limited ecosystems such as the Amazon basin has implications for long-term productivity. We used a 100-year replicated observational chronosequence of primary forest conversion to pasture, as well as a 13-year-old secondary forest, to test land use change and duration effects on soil P dynamics in the Amazon basin. By combining sequential extraction and P K-edge X-ray absorption near edge structure (XANES) spectroscopy with soil phosphatase activity assays, we assessed pools and process rates of P cycling in surface soils (0-10 cm depth). Deforestation caused increases in total P (135-398 mg kg-1 ), total organic P (Po ) (19-168 mg kg-1 ), and total inorganic P (Pi ) (30-113 mg kg-1 ) fractions in surface soils with pasture age, with concomitant increases in Pi fractions corroborated by sequential fractionation and XANES spectroscopy. Soil non-labile Po (10-148 mg kg-1 ) increased disproportionately compared to labile Po (from 4-5 to 7-13 mg kg-1 ). Soil phosphomonoesterase and phosphodiesterase binding affinity (Km ) decreased while the specificity constant (Ka ) increased by 83%-159% in 39-100y pastures. Soil P pools and process rates reverted to magnitudes similar to primary forests within 13 years of pasture abandonment. However, the relatively short but representative pre-abandonment pasture duration of our secondary forest may not have entailed significant deforestation effects on soil P cycling, highlighting the need to consider both pasture duration and reforestation age in evaluations of Amazon land use legacies. Although the space-for-time substitution design can entail variation in the initial soil P pools due to atmospheric P deposition, soil properties, and/or primary forest growth, the trend of P pools and process rates with pasture age still provides valuable insights.

Quantifying Uncertainties in Sequential Chemical Extraction of Soil Phosphorus Using XANES Spectroscopy.

Sequential chemical extraction has been widely used to study soil phosphorus (P) dynamics and inform nutrient management, but its efficacy for assigning P into biologically meaningful pools remains unknown. Here, we evaluated the accuracy of the modified Hedley extraction scheme using P K-edge X-ray absorption near-edge structure (XANES) spectroscopy for nine carbonate-free soil samples with diverse chemical and mineralogical properties resulting from different degrees of soil development. For most samples, the extraction markedly overestimated the pool size of calcium-bound P (Ca-P, extracted by 1 M HCl) due to (1) P redistribution during the alkaline extractions (0.5 M NaHCO3 and then 0.1 M NaOH), creating new Ca-P via formation of Ca phosphates between NaOH-desorbed phosphate and exchangeable Ca2+ and/or (2) dissolution of poorly crystalline Fe and Al oxides by 1 M HCl, releasing P occluded by these oxides into solution. The first mechanism may occur in soils rich in well-crystallized minerals and exchangeable Ca2+ regardless of the presence or absence of CaCO3, whereas the second mechanism likely operates in soils rich in poorly crystalline Fe and Al minerals. The overestimation of Ca-P simultaneously caused underestimation of the pools extracted by the alkaline solutions. Our findings identify key edaphic parameters that remarkably influenced the extractions, which will strengthen our understanding of soil P dynamics using this widely accepted procedure.

X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces.

Sulfate adsorption on mineral surfaces is an important environmental chemical process, but the structures and respective contribution of different adsorption complexes under various environmental conditions are unclear. By combining sulfur K-edge XANES and EXAFS spectroscopy, quantum chemical calculations, and surface complexation modeling (SCM), we have shown that sulfate forms both outer-sphere complexes and bidentate-binuclear inner-sphere complexes on ferrihydrite surfaces. The relative fractions of the complexes vary with pH, ionic strength (I), and sample hydration degree (wet versus air-dried), but their structures remained the same. The inner-sphere complex adsorption loading decreases with increasing pH while remaining unchanged with I. At both I = 0.02 and 0.1 M, the outer-sphere complex loading reaches maximum at pH ∼5 and then decreases with pH, whereas it monotonically decreases with pH at I = 0.5 M. These observations result from a combination of the ionic-strength effect, the pH dependence of anion adsorption, and the competition between inner- and outer-sphere complexation. Air-drying drastically converts the outer-sphere complexes to the inner-sphere complexes. The respective contributions to the overall adsorption loading of the two complexes were directly modeled with the extended triple layer SCM by implementing the bidentate-binuclear inner-sphere complexation identified in the present study. These findings improve our understanding of sulfate adsorption and its effects on other environmental chemical processes and have important implications for generalizing the adsorption behavior of anions forming both inner- and outer-sphere complexes on mineral surfaces.

Sulfate Local Coordination Environment in Schwertmannite.

Schwertmannite, a nanocrystalline ferric oxyhydroxy-sulfate mineral, plays an important role in many environmental geochemical processes in acidic sulfate-rich environments. The sulfate coordination environment in schwertmannite, however, remains unclear, hindering our understanding of the structure, formation, and environmental behavior of the mineral. In this study, sulfur K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopic analyses in combination with infrared spectroscopy were used to determine the sulfate local atomic environment in wet and air-dried schwertmannite samples after incubation at various pHs and ionic strengths. Results indicate that sulfate exists as both inner- and outer-sphere complexes in schwertmannite. Regardless of the sample preparation conditions, the EXAFS-determined S-Fe interatomic distances are 3.22-3.26 Å, indicative of bidentate-binuclear sulfate inner-sphere complexes. XANES spectroscopy shows that the proportion of the inner-sphere complexes decreases with increasing pH for both wet and dried samples and that the dried samples contain much more inner-sphere complexes than the wet ones at any given pH. Assuming that schwertmannite is a distorted akaganéite-like structure, the sulfate inner-sphere complexation suggests that, the double chains of the edge-sharing Fe octahedra, enclosing the tunnel, must contain defects, on which reactive singly-Fe coordinated hydroxyl functional groups form for ligand exchange with sulfate. The drying effect suggests that the tunnel contains readily exchangeable H2O molecules in addition to sulfate ions.

Saltwater intrusion increases phosphorus abundance and alters availability in coastal soils with implications for future sea level rise.

Sea level rise (SLR) promotes saltwater intrusion (SWI) into coastal soils globally at an increasing rate, impacting phosphorus (P) dynamics and adjacent water quality. However, how SWI influences P molecular speciation and availability in coastal soils remains poorly understood. By using a space-for-time substitution strategy, we evaluated the SWI impacts on P transformation along a SWI gradient at the Rehoboth Inland Bay, which consists of five sampling locations along a transect representing different SWI degrees. Soils were analyzed at the macro- and micro-scale using X-ray absorption near edge spectroscopy (XANES) and the modified Hedley fractionation. With increasing distance from the Bay, soil salinity (29.3-0.07 mmhos cm-1), the proportion of Fe3+ to total Fe, and P concentrations decreased. The fractionation showed that recalcitrant P was dominant (86.9-89.5% of total P). With increasing SWI, labile P increased gradually, reached a plateau, and then decreased sharply. Bulk XANES spectroscopy showed that soil P was likely dominated by iron and aluminum-associated P (Fe/Al-P), regardless of the SWI degree. Hence, with increasing SWI, P increasingly accumulated in a recalcitrant pool, mainly as Fe/Al-P. µ-XANES spectroscopy revealed that calcium-associated P (Ca-P) existed in P-rich spots of the greatest SWI soil while Al-P occurred in P-rich spots of the low SWI soil, consistent with the greater HCl-P (presumably Ca-P) in the former soil. Overall, results demonstrate that SWI impacts P availability and environmental risk in coastal soils depending on the degree of SWI. These findings have important implications for understanding soil P cycling and availability in SLR-impacted coastal areas.

Environmental geochemistry of an abandoned mercury mine in Yanwuping, Guizhou Province, China.

The distribution of mercury (Hg) and methylmercury (MeHg) in paddy soil and rice grain (polished), and Hg in surface waters and gaseous elemental Hg (GEM) in atmosphere at the Yanwuping Hg mining district (YMM), Guizhou Province, China was investigated. Results exhibited high total Hg (Hg(T)) and MeHg concentrations in soil at sites adjacent to calcine pile and tailings, and ranged from 5.6 to 240mgkg(-1) and 0.66 to 7.3µgkg(-1), respectively. Concentrations of Hg(T) in rice ranged from 10 to 45µgkg(-1), and high MeHg concentrations were also observed ranging from 3.2 to 39µgkg(-1). The elevated Hg(T) and MeHg concentrations in soil in the vicinity of calcine pile and tailings reflected in high MeHg concentrations in rice. Those data were significantly correlated with MeHg concentration in soil confirming that soil is the major source of MeHg in rice. The highest Hg concentrations in water, otherwise rather low, ranging from 3.8 to 51ngl(-1) for Hg(T) and of 0.14 to 2.7ngl(-1) for MeHg(T), were found at the proximity of calcine pile suggesting that untreated mine wastes are the principal source of Hg in the nearby area. Huge emissions of GEM were also detected from calcines affecting the whole area, ranging from 12 to 180ngm(-3) with an average of 46±35ngm(-3). The distribution patterns of Hg and MeHg observed in the environmental compartments suggest an elevated contamination of Hg in the region. Elevated high MeHg concentrations in rice might pose a potential health risk to local populations.

The impacts of aging pH and time of acid mine drainage solutions on Fe mineralogy and chemical fractions of heavy metals in the sediments.

Fe (oxyhydr)oxides are the main components that accumulate heavy metals (HMs) in the acid mine drainage (AMD) sediments, but how the aging pH and time of AMD solution affects the Fe mineralogy and HMs speciation remains ambiguous. Herein, we determined the impacts of aging pH and time on the Fe mineralogy and chemical fractions of HMs in the sediments from Dabaoshan mining area using mineral characterizations, chemical extraction, and AMD solution incubation. For the natural AMD sediments, jarosite and goethite are the major Fe (oxyhydr)oxides in sample S1 with solution pH 2.68, while schwertmannite is dominant in sample S2 with solution pH 6.78, co-existing minor ferrihydrite. With increasing the AMD solution pH, the total contents of HMs (expect for As) and the reducible fraction of HMs (expect for Pb) in the sediments both increase. The HMs of Mn, Zn, Ni, and Cd are mainly associated with Fe (oxyhydr)oxides, while Pb possibly exists as Pb-bearing minerals (e.g., PbSO4) in the sediments. The oxidizable fraction of all HMs is negligible in both sediments. When the AMD solution of S1 was aged at different pHs, schwertmannite is dominant initially at all pHs, with a higher crystallinity being at a lower pH. With increasing aging time, the pre-formed schwertmannite transforms to goethite and jarosite at pH ≤ 3, while it keeps stable at pH 5 and 7 due to the accumulation of more HMs. These new insights are essential to assess the mobility and availability of HMs in the AMD-affected areas.

Weir building: A potential cost-effective method for reducing mercury leaching from abandoned mining tailings.

To mitigate mercury (Hg) pollution and reduce Hg downstream transportation, a weir was designed by a river system that had been inflicted by leachate from the slagheap of the Yanwuping Hg mine in Wanshan Hg mining area. A whole year monitoring of Hg species was conducted, and the efficiency of Hg reduction by the weir application was evaluated. The Hg concentrations in the river water were significantly higher in the wet season than in the dry season. Waterflow was confirmed to be the main driving factor for Hg mobilization and transportation, and an episode study revealed that most Hg was released in times of storms. Increased monitoring and preventive maintenance measures need to be taken on barriers in advance of storms. A large proportion of the total Hg (THg) and methylmercury (MeHg) is associated to particles. During the study period, approximately 412 g THg and 4.04 g total MeHg (TMeHg) were released from the YMM slagheap, of which 167 g THg and 1.15 g TMeHg were retained by the weir. Annually, 40.4% THg and 38.4% TMeHg was retained by the weir. Weir construction is considered as a potential cost-effective measure to mitigate Hg in river water and should be promoted and extended in the future after optimization.

New insights into the chemical forms of extremely high methylmercury in songbird feathers from a contaminated site.

The chemical forms of mercury (Hg), particularly methylmercury (MeHg), in songbird feathers from an abandoned mining region were analyzed via X-ray absorption near-edge structure analysis (XANES). In feathers, proportions of MeHg as total mercury (75.6-100%) quantified by the XANES were directly comparable to the chemical extraction values (74.1-95.9%). Most of MeHg were bound with cysteine (Cys) and reduced glutathione (GSH), whereas inorganic mercury (IHg) was mainly bound with GSH. These results were consistent with those found in fish muscles and human hairs of both fish consumers and occupational Hg exposure populations. Our study suggested that chemical forms and speciation of Hg were highly dependent on the exposure sources and food consumption, respectively. Bird feathers were able to selectively accumulate MeHg due to their special binding ways. However, detailed mechanisms of Hg accumulation in bird feathers remain to be further elucidated.

The local impact of a coal-fired power plant on inorganic mercury and methyl-mercury distribution in rice (Oryza sativa L.).

Emission from coal-fired power plants is one of the major anthropogenic sources of mercury (Hg) in the environment, because emitted Hg can be quickly deposited nearby the source, attention is paid to the effects of coal-burning facilities on levels of toxic methyl-mercury (MeHg) in biota near such sources. Since rice is an agricultural crop that can bio-accumulate MeHg, the potential effects of a large Hg-emitting coal-fired power plant in Hunan Province, China on both inorganic Hg (Hg(II)) and MeHg distributions in rice was investigated. Relatively high MeHg (up to 3.8 µg kg-1) and Hg(II) (up to 22 µg kg-1) concentrations were observed in rice samples collected adjacent to the plant, suggesting a potential impact of Hg emission from the coal fired power plant on the accumulation of Hg in rice in the area. Concentrations of MeHg in rice were positively correlated with soil MeHg, soil S, and gaseous elemental Hg (GEM) in ambient air. Soil MeHg was the most important factor controlling MeHg concentrations in rice. The methylation of Hg in soils may be controlled by factors such as the chemical speciation of inorganic Hg, soil S, and ambient GEM.

Transportation and transformation of mercury in a calcine profile in the Wanshan Mercury Mine, SW China.

Calcination of Hg ores has resulted in serious contamination of mercury (Hg) in the environment. To understand the mobilization of Hg in the calcine pile, the speciation of Hg in a profile of a large calcine pile in the Wanshan Mercury Mine, SW China was investigated using the X-ray absorption spectroscopy (XANES), to understand the mobilization of Hg in the calcine pile. Higher concentrations of Hg were observed at the 30-50 cm depth of the profile, corresponding to a cemented layer. This layer is observed in the entire pile, and was formed due to cementation of calcines. Hg species in calcines include cinnabar (α-HgS), metacinnabar (ß-HgS), elemental Hg(0), and minor mercuric chloride (HgCl2), but these Hg species show dramatic changes in the profile. Variations in Hg speciation suggest that extensive mobilization of Hg can occur during weathering processes. We show that the cemented layer can prevent the leaching of Hg and the emission of Hg(0) from the pile. High MeHg concentrations were found near the cemented layer, indicating Hg methylation occurs. This study provides important insights into the environmental risk of Hg in mining areas.

Understanding the paradox of selenium contamination in mercury mining areas: high soil content and low accumulation in rice.

Rice is an important source of Se for billions of people throughout the world. The Wanshan area can be categorized as a seleniferous region due to its high soil Se content, but the Se content in the rice in Wanshan is much lower than that from typical seleniferous regions with an equivalent soil Se level. To investigate why the Se bioaccumulation in Wanshan is low, we measured the soil Se speciation using a sequential partial dissolution technique. The results demonstrated that the bioavailable species only accounted for a small proportion of the total Se in the soils from Wanshan, a much lower quantity than that found in the seleniferous regions. The potential mechanisms may be associated with the existence of Hg contamination, which is likely related to the formation of an inert Hg-Se insoluble precipitate in soils in Wanshan.