Effects of long-term irrigation with treated wastewater. Part II: Role of organic carbon on Cu,Pb and Cr behaviour

The long-term impact of irrigation on a Mediterranean sandy soil irrigated with treated wastewater (TWW) since 1980 was evaluated. The main soil properties (CEC, pH, size distribution, exchangeable cations and chloride, hydraulic conductivity) as well as the organic matter and Cu, Cr and Pb speciation in an irrigated soil and a non-irrigated control soil at various soil depths were monitored and compared during a 2 year experiment. In this second part, we focused on Cu, Cr and Pb behaviour in relation with soil organic carbon (SOC). Soil samples were collected every 3 months during 2 years at the depths 0–20, 20–40 and 40–60 cm and were analysed for exchangeable and total metals, organic carbon content, metal sequential extraction and humic substances – Humic Acids (HA), Fulvic Acids (FA) and Non-Humified Fraction (NHF). Long-term irrigation with a domestic treated wastewater (TWW) may be considered safe with regard to trace metal accumulation in soil. Irrigation lowered the HA and NHF fractions of SOC and made the FA fraction more mobile. Cu bound preferentially to the SOC fraction, Cr was found mainly in the reducible fraction and Pb was bound to all fractions indiscriminately. Cu exhibited a high affinity for the HA fraction, while Pb and Cr had a high affinity for the FA fraction, which indicates a greater mobility of the organically-bound Pb and Cr than of the organically-bound Cu. Evaluation of the potential metal mobility has to take into account not only the usual speciation between labile, reducible and oxidisable fractions, but also the nature of the SOC responsible for the oxidisable fraction.     

Size distributions of hydrocarbons in suspended particles from the Yellow River

Suspended particle samples from the Yellow River estuary were sorted into five grain size fractions to explore the effect of grain size distribution on organic matter content and composition. The n-alkanes and PAHs were determined for each size fraction. PAHs and n-alkanes were more abundant in the finer fractions and the loading decreases steadily with increasing of grain size. However, the total n-alkanes or PAHs normalized to organic C were lower in the smaller size fractions than those in the larger size fractions, suggesting n-alkanes or PAHs may be diluted by the addition of organic matter or gradually decreased by degradation in the smaller size fractions. The particulate n-alkanes in the Yellow River estuary consist of a mixture of compounds from terrigenous and riverine biogenic n-alkanes and more biogenic n-alkanes accumulate in finer particles. Particulate PAHs are related to combustion/pyrolysis processes of coal/wood, and the relative contribution of petrogenic PAHs increase with increasing grain size. The total particulate n-alkane and PAH discharges passing the Lijin Station are about 3.94 t d⁻¹ and 0.52 t d⁻¹, respectively. Fine particles (<32 μm) play a significant role in organic matter transfer.     

Acid-base and copper-binding properties of three organic matter fractions isolated from a forest floor soil solution

Vast amounts of knowledge about the proton- and metal-binding properties of dissolved organic matter (DOM) in natural waters have been obtained in studies on isolated humic and fulvic (hydrophobic) acids. Although macromolecular hydrophilic acids normally make up about one-third of DOM, their proton- and metal-binding properties are poorly known. Here, we investigated the acid-base and Cu-binding properties of the hydrophobic (fulvic) acid fraction and two hydrophilic fractions isolated from a soil solution. Proton titrations revealed a higher total charge for the hydrophilic acid fractions than for the hydrophobic acid fraction. The most hydrophilic fraction appeared to be dominated by weak acid sites, as evidenced by increased slope of the curve of surface charge versus pH at pH values above 6. The titration curves were poorly predicted by both Stockholm Humic Model (SHM) and NICA-Donnan model calculations using generic parameter values, but could be modelled accurately after optimisation of the proton-binding parameters (pH ? 9). Cu-binding isotherms for the three fractions were determined at pH values of 4, 6 and 9. With the optimised proton-binding parameters, the SHM model predictions for Cu binding improved, whereas the NICA-Donnan predictions deteriorated. After optimisation of Cu-binding parameters, both models described the experimental data satisfactorily. Iron(III) and aluminium competed strongly with Cu for binding sites at both pH 4 and pH 6. The SHM model predicted this competition reasonably well, but the NICA-Donnan model underestimated the effects significantly at pH 6. Overall, the Cu-binding behaviour of the two hydrophilic acid fractions was very similar to that of the hydrophobic acid fraction, despite the differences observed in proton-binding characteristics. These results show that for modelling purposes, it is essential to include the hydrophilic acid fraction in the pool of ‘active’ humic substances.     

In situ and laboratory investigation of the alteration of Boom Clay (Oligocene) at the air–geological barrier interface within the Mol underground facility (Belgium): Consequences on kerogen and bitumen compositions

The Boom Clay formation (Oligocene) is studied as a reference host rock for methodological studies on deep geological disposal of radioactive waste. During excavation of galleries within the Clay formation (HADES underground research facility, Mol, Belgium), the physico-chemical conditions are significantly modified as an air–clay interface is created. In order to study the long-term impact of the air–clay contact on the organic matter contained in the Boom Clay, two types of samples were studied: (1) a reference series of clay samples having been in contact with the atmosphere of the HADES gallery for increasing times up to several years and (2) unaltered clay samples submitted to artificial oxidation in a ventilated oven at 80 °C. The evolution of geochemical data of the two series was compared using Rock-Eval pyrolysis, GC–MS and size exclusion chromatography. The organic matter of the unaltered clays sampled in the HADES galleries is dominated by type III kerogen (terrestrial) with some contribution of type II (marine) and is thermally immature. The evolution of geochemical parameters during air alteration for the two series are very similar. They show progressive oxidation of kerogen accompanied by the release of bitumen enriched in low molecular weight constituents. Molecular analysis evidences the presence of a complex mixture of aliphatic and aromatic O-bearing compounds, inherited from the degradation of kerogen as well as from the clay catalyzed oxidation of the bitumen. These results show that (1) air oxidation is a major process in the in situ alteration of the organic matter of Boom Clay within the HADES galleries, (2) laboratory oxidation experiments at 80 °C yield similar results as in situ air alteration of Boom Clay and (3) artificial air oxidation may be used to assess the long term exposure of the organic matter to air.     

Detection of manure-derived organic compounds in rivers draining agricultural areas of intensive manure spreading

It is essential to have suitable tools able to trace the fate of manure organic matter in the environment to assess whether manure disposal on the soils of catchments could affect the organic quality of rivers. Sterol compounds – mainly expressed as C_29 + 28/C₂₇ and 5β/C₂₇ ratios – have been shown to be specific molecular tracers of pig, dairy and poultry manures in soils. The objective of this study was to measure C_29 + 28/C₂₇ and 5β/C₂₇ ratios in five Brittany rivers (Elorn, Yar, Léguer, Min Ran and Couesnon) draining agricultural catchments receiving massive annual inputs of pig, poultry and dairy manures and compare these ratios with ratios published for enriched soils and manure samples. The particulate organic fractions from the studied rivers yielded steroid signatures typical of animal manures. More specifically, a stanol compound diagnostic of pig slurry – the 5β-stanol known as coprostanol – was found to be very widespread, with particularly high concentrations in one of the rivers (Elorn). The C_29 + 28/C₂₇ and 5β/C₂₇ ratios of the particulate fractions of the rivers were compared with ratios measured directly in pig, dairy and poultry manure samples, as well as with the breeding activities on river catchments. These comparisons show that the steroid profiles of the five investigated rivers correlate closely with the types of manure (i.e. pig, poultry or dairy) spread on soils in their catchments. For instance, the C_29 + 28/C₂₇ and 5β/C₂₇ ratios in the Elorn river are similar to the values typical of pig slurry (e.g. 5β/C₂₇ > 4); compared with other catchments, the soils in this area receive by far the largest amount of pig slurry. By contrast, the Yar river drains a catchment receiving only poultry and dairy manures, and its soils exhibit C_29 + 28/C₂₇ and 5β/C₂₇ ratios similar to those of dairy and poultry manures (e.g. 5β/C₂₇ ∼ 1). Thus, this study indicates that the organic quality of rivers is modified in catchments where there is intense manure spreading on soils. It also provides evidence that rivers draining areas receiving different manure types may exhibit differences in the long-term evolution of their OM content. Indeed, two of the investigated river catchments receive dominantly dairy and poultry manure, and exhibit clear long-term upward trends in OM. On the other hand, one catchment receiving high proportions of pig slurry clearly shows a long-term downward trend in OM contents. A survey of the literature shows that the relative amount of OM and N received by soils in agricultural catchments could be the key parameter in determining the direction of the long-term OM trend of the river, rather than the absolute amount and/or type of manure that is applied to the soil. In any case, the present study suggests that sterol/stanol compounds may be of diagnostic value in determining whether a stream or a river is undergoing contamination by manure-derived organic matter.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Fate and groundwater impacts of produced water releases at OSPER “B” site,Osage County,Oklahoma

For the last 5 a, the authors have been investigating the transport, fate, natural attenuation and ecosystem impacts of inorganic and organic compounds in releases of produced water and associated hydrocarbons at the Osage-Skiatook Petroleum Environmental Research (OSPER) “A” and “B” sites, located in NE Oklahoma. Approximately 1.0 ha of land at OSPER “B”, located within the active Branstetter lease, is visibly affected by salt scarring, tree kills, soil salinization, and brine and petroleum contamination. Site “B” includes an active production tank battery and adjacent large brine pit, two injection well sites, one with an adjacent small pit, and an abandoned brine pit and tank battery site. Oil production in this lease started in 1938, and currently there are 10 wells that produce 0.2–0.5 m³/d (1–3 bbl/d) oil, and 8–16 m³/d (50–100 bbl/d) brine. Geochemical data from nearby oil wells show that the produced water source is a Na–Ca–Cl brine (∼150,000 mg/L TDS), with high Mg, but low SO₄ and dissolved organic concentrations. Groundwater impacts are being investigated by detailed chemical analyses of water from repeated sampling of 41 boreholes, 1–71 m deep. The most important results at OSPER “B” are: (1) significant amounts of produced water from the two active brine pits percolate into the surficial rocks and flow towards the adjacent Skiatook reservoir, but only minor amounts of liquid petroleum leave the brine pits; (2) produced-water brine and minor dissolved organics have penetrated the thick (3–7 m) shale and siltstone units resulting in the formation of three interconnected plumes of high-salinity water (5000–30,000 mg/L TDS) that extend towards the Skiatook reservoir from the two active and one abandoned brine pits; and (3) groundwater from the deep section of only one well, BR-01 located 330 m upslope and west of the site, appear not to be impacted by petroleum operations.     

Terrigenous organic matter sources in mid-pleistocene sediments from the orphan knoll,Northwest Atlantic Ocean

The concentration and composition of lignin-derived phenols, which are often used as biomarkers for terrigenous organic matter (OM) inputs, were examined in North Atlantic Ocean sediments from IODP core U1302A (50°9.985′N, 45°38.271′W, 3568 m water depth), Orphan Knoll, 650 km NE of St. John’s, Newfoundland, Canada for the period of ca. 1100–810 ka BP. Lignin-derived phenols were extracted from sediments using CuO oxidation which yielded eight characteristic phenols. The majority of sediments have low syringyl phenol to vanillyl phenol (S/V) ratios and high cinnamyl phenol to vanillyl phenol (C/V) ratios, suggesting predominant concentrations of gymnosperm-derived organic matter inputs from adjacent continents (most likely eastern Canada and possibly southern Greenland). The S/V values were lower for the period of ca. 958–840 ka BP relative to ca. 1090–1078, 1042–958 and 840–818 ka BP, indicating fluctuations in the proportion of angiosperm- and gymnosperm-derived lignin delivery to the ocean. The greater fraction of gymnosperms for the period of 958–840 ka BP likely reflects the response of vegetation in source regions to climate cooling in the early part of the mid-Pleistocene. Lignin-derived phenol concentrations also displayed high variability during the investigated period, which did not show positive correlations with magnetic susceptibility or Gamma Ray Attenuation density. Considering that a fundamental climate change (41–100 ka cyclicity) occurred within the mid-Pleistocene, large variations in abundance and composition of lignin-derived phenols in core U1302A is likely indicative of dynamic environmental conditions, reflected by the variability in both concentrations and types of vegetation on adjacent continents and/or different mechanisms to transport terrigenous organic matter to the deep ocean.     

Determination of sulfide ligands and association with natural organic matter

Group B metals, such as Hg, Cu, Ag, Pb and Cd bind strongly to reduced inorganic and organic S(II−) ligands. These S(II−) ligands, stable in oxic waters for significant periods of time, occur at the <1–100 s nM concentrations. It is hypothesized that S(II−) ligands are stabilized as Cu–S molecules associated with organic matter by multi-ligand binding or in nano-pore encapsulations in organic matter. S(II−) ligands are estimated by two methods: purge/trap analysis as Cr-reducible sulfide (CRS), and strong ligand (SL_T) from a competitive ligand titration with Ag(I). The CRS/SL_T ratio is nearly one for selected samples. CRS correlates reasonably well (r² ∼ 0.5) with organic C with a slope of 14.6 nM per mg C. The conditional binding constant of Ag–SL is 11.3 for effluent associated with waste-water and decreases for river waters from about 12–8.8 as the strong sites are occupied with Ag(I).     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

A critical review of three methods used for the measurement of mercury (Hg)-dissolved organic matter stability constants

Three experimental techniques – ion exchange, liquid–liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE–SPE) – were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg²⁺) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid–liquid extraction method was found to be complicated by the ability of Hg–DOM complexes to partition into the organic phase. The CLE–SPE method was found to be the most suitable of these methods for the measurement of Hg–DOM stability constants. Stability constants for DOM isolates measured using the CLE–SPE method at environmentally relevant Hg:DOM ratios were log K = 25–30 (M⁻¹). These values are consistent with the strong Hg²⁺ binding expected for reduced S-containing binding sites.     

Contamination of surface waters by mining wastes in the Milluni Valley (Cordillera Real,Bolivia): Mineralogical and hydrological influences

This study is one of very few dealing with mining waste contamination in high altitude, tropical-latitude areas exploited during the last century. Geochemical, mineralogical and hydrological characterizations of potentially harmful elements (PHEs) in surface waters and sediments were performed in the Milluni Valley (main reservoir of water supply of La Paz, Bolivia, 4000 m a.s.l.), throughout different seasons during 2002–2004 to identify contamination sources and sinks, and contamination control parameters. PHE concentrations greatly exceeded the World Health Organization water guidelines for human consumption. The very acidic conditions, which resulted from the oxidation of sulfide minerals in mining waste, favoured the enrichment of dissolved PHEs (Cd > Zn ? As ? Cu ∼ Ni > Pb > Sn) in surface waters downstream from the mine. Stream and lake sediments, mining waste and bedrock showed the highest PHE content in the mining area. With the exception of Fe, the PHEs were derived from specific minerals (Fe, pyrite; Zn, Cd, sphalerite, As, Fe, arsenopyrite, Cu, Fe, chalcopyrite, Pb, galena, Sn, cassiterite), but the mining was responsible for PHEs availability. Most of the PHEs were extremely mobile (As > Fe > Pb > Cd > Zn ∼ Cu > Sn) in the mining wastes and the sediments downstream from the mine. pH and oxyhydroxides mainly explained the contrasted availability of Zn (mostly in labile fractions) and As (associated with Fe-oxyhydroxides). Unexpectedly, Pb, Zn, As, and Fe were significantly attenuated by organic matter in acidic lake sediments.     

Alteration of As-bearing phases in a small watershed located on a high grade arsenic-geochemical anomaly (French Massif Central)

At a watershed scale, sediments and soil weathering exerts a control on solid and dissolved transport of trace elements in surface waters and it can be considered as a source of pollution. The studied subwatershed (1.5 km²) was located on an As-geochemical anomaly. The studied soil profile showed a significant decrease of As content from 1500 mg kg⁻¹ in the 135–165 cm deepest soil layer to 385 mg kg⁻¹ in the upper 0–5 cm soil layer. Directly in the stream, suspended matter and the <63 μm fraction of bed sediments had As concentrations greater than 400 mg kg⁻¹. In all these solid fractions, the main representative As-bearing phases were determined at two different observation scales: bulk analyses using X-ray absorption structure spectroscopy (XAS) and microanalyses using scanning electron microscope (SEM) and associated electron probe microanalyses (EPMA), as well as micro-Raman spectroscopy and synchrotron-based micro-scanning X-ray diffraction (μSXRD) characterization. Three main As-bearing phases were identified: (i) arsenates (mostly pharmacosiderite), the most concentrated phases As in both the coherent weathered bedrock and the 135–165 cm soil layer but not observed in the river solid fraction, (ii) Fe-oxyhydroxides with in situ As content up to 15.4 wt.% in the deepest soil layer, and (iii) aluminosilicates, the least concentrated As carriers. The mineralogical evolution of As-bearing phases in the soil profile, coupled with the decrease of bulk As content, may be related to pedogenesis processes, suggesting an evolution of arsenates into As-rich Fe-oxyhydroxides. Therefore, weathering and mineralogical evolution of these As-rich phases may release As to surface waters.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

Diagenetic processes on metals in hypersaline mudflat sediments from a subtropical saltmarsh (SE Gulf of California): Postdepositional mobility and geochemical fractions

To understand the biogeochemical cycles of trace metals (Cd, Cu, Fe, Mn, Ni and Zn) in a hypersaline subtropical marsh, geochemical studies of both interstitial and solid phases were conducted on sediment cores from Chiricahueto marsh, SE Gulf of California. The sequential extraction procedure proposed by Tessier was used to estimate the percentages of the metals present in each geochemical phase of the sediment. Metal concentrations in the solid phase were found to be enriched in the upper layers and mainly associated with reactive fractions such as organic matter, Fe–Mn oxyhydroxides and carbonates (46–74% of Ni, Mn and Cd, and 11–19% of Cu and Zn). Principal factor analysis (PFA) and Spearman correlation analysis revealed a strong positive association of metals and their reactive phases with OC (the diagenetic component), and a negative or non-association with the mud content, Al, Fe and Li (the lithogenic component). Diagenetically released metals are mainly mobilized within hypersaline sediments by buoyancy transport (>90% of total flux) in response to an extreme salinity gradient by input of fresh groundwater (3–6 psu cm⁻¹). The molecular diffusion due to the gradient of metals in porewater (maximum and higher levels at 5–7 and below 20 cm depth, respectively) is significantly less important to the advective transport. Most of the metals mobilized by diffusion–advection processes are re-precipitated in the sediments by authigenic minerals, only <10% of most metals are extruded out to the overlying water column. Authigenic accumulation rates were estimated as 1.42–7.09 mg m⁻² a⁻¹ for Cd; 58.8–378 for Cu; 6922–17,985 for Fe; 38.2–345 for Mn; 20.8–263 for Ni; and 282–2956 mg m⁻² a⁻¹ for Zn. The Mn–Fe oxyhydroxides (40–85% of reactive metals) in the upper oxic–suboxic layers (<5 cm below surface) and sulfide minerals (75–97%) in anoxic sediment layers (7–18 cm) constitute the main scavengers for metals.     

Organic matter compositions and DOM release from the sediments of the shallow lakes in the middle and lower reaches of Yangtze River region, China

The contents of different organic matter components and dissolved organic matter (DOM) release kinetics of the sediments from the middle and lower reaches of the Yangtze River region were investigated, and their relationships discussed. The results show that organic C (OC) ranged from 8.14 to 43.65 g kg⁻¹, dissolved organic C (DOC) from 0.38 to 1.38 g kg⁻¹, active organic C (AOC) from 1.12 to 4.45 g kg⁻¹, heavy fraction organic C (HFOC) from 6.86 to 39.08 g kg⁻¹, accounting for 2.42-9.34%, 8.66-29.72% and 84.29-93.18% of OC, respectively. With increasing of OC content the ratios of DOC to OC and AOC to OC decreased. The contents of AOC, DOC, light fraction organic C (LFOC) and their contribution ratios to OC in studied sediments were higher than those reported in soils. The DOM release process of the studied sediments includes rapid and slow stages, and the rapid release occurred within 30 min, mainly in 5 min. The DOM release kinetic data in this investigation can be best fitted by the Power Function model. The correlations between total N (TN), total P (TP), OC, DOC, AOC, LFOC, HFOC and the DOM release kinetic parameters (k, c, a, b, rate₃₀) of the sediments were significant. There were also significant correlations between TN, TP, OC, DOC, LFOC and HFOC in sediments. So the DOM release from sediment was not only related to the OC content, but also related to the organic matter composition characteristics, especially the contents of DOC, AOC and LFOC.     

Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

Mercury is a global contaminant of concern due to its transformation by microorganisms to form methylmercury, a toxic species that accumulates in biological tissues. The effect of dissolved organic matter (DOM) isolated from natural waters on reactions between mercury(II) (Hg) and sulfide (S(-II)) to form HgS_(s) nanoparticles across a range of Hg and S(-II) concentrations was investigated. Hg was equilibrated with DOM, after which S(-II) was added. Dissolved Hg (Hg_aq) was periodically quantified using ultracentrifugation and chemical analysis following the addition of S(-II). Particle size and identity were determined using dynamic light scattering and X-ray absorption spectroscopy. S(-II) reacts with Hg to form 20 to 200 nm aggregates consisting of 1-2 nm HgS_(s) subunits that are more structurally disordered than metacinnabar in the presence of 2 × 10⁻⁹ to 8 × 10⁻⁶ M Hg and 10 (mg C) L⁻¹ DOM. Some of the HgS_(s) nanoparticle aggregates are subsequently dissolved by DOM and (re)precipitated by S(-II) over periods of hours to days. At least three fractions of Hg-DOM species were observed with respect to reactivity toward S(-II): 0.3 μmol reactive Hg per mmol C (60 percent), 0.1 μmol per mmol C (20 percent) that are kinetically hindered, and another 0.1 μmol Hg per mmol C (20 percent) that are inert to reaction with S(-II). Following an initial S(-II)-driven precipitation of HgS_(s), HgS_(s) was dissolved by DOM or organic sulfur compounds. HgS_(s) formation during this second phase was counterintuitively favored by lower S(-II) concentrations, suggesting surface association of DOM moieties that are less capable of dissolving HgS_(s). DOM partially inhibits HgS_(s) formation and mediates reactions between Hg and S(-II) such that HgS_(s) is susceptible to dissolution. These findings indicate that Hg accessibility to microorganisms could be controlled by kinetic (intermediate) species in the presence of S(-II) and DOM, undermining the premise that equilibrium Hg species distributions should correlate to the extent or rate of Hg methylation in soils and sediments.     

Biogeochemical processes in a clay formation in situ experiment: Part C - Organic contamination and leaching data

Data interpretation of the Porewater Chemistry (PC) experiment at the Mont Terri Rock Laboratory has led to unexpected observations of anaerobic microbial processes which caused important geochemical perturbations of the Opalinus Clay water in the borehole. The increases of acetate to 146 mg C/L, of DIC to 109 mg C/L and of CH₄ to 0.5 mg C/L were unexpected and could not be explained without the presence of a C source in the system. The organic C fuelling the observed microbial activity was until then unknown. Leaching tests were performed on several polymers used for the fabrication of the PC equipment to identify the source of organic matter (OM). Polyethylene (PE) appears to be very inert and does not release detectable concentrations of dissolved organic C (DOC) (<1 ppb) into the water. Polyurethane (PU) leaches out a dozen different organic compounds accounting for only 13 μg DOC/g PU. Under the conditions of the leaching tests, 1 g of polyamide (PA, Nylon) also releases ∼512 μg of the plasticizer N-Butyl-Benzene-Sulfonamide (NBBS). Soaking tests with polyethylene samples immersed in acetone under conditions similar to those used to remove grease spots on the porous PE filter prior to installation showed that acetone could have been trapped in the PE filter, corresponding to an initial concentration of 1.5 g acetone/L of water. However, the accumulated amount of organic C taken into account from all these components was insufficient to satisfactorily explain the observed microbially mediated reducing perturbation. Finally, large amounts of dissolved organic C were found to be released in the system by the jelly polymer filling the reference compartment of the pH and E_h electrodes permanently installed over 5 years in flow-through cells on the water circulation loop of the PC experiment. Glycerol was further identified by chromatographic analysis as the main organic compound released by the electrodes. From the analysis results, as well as from the geochemical calculations, the most likely primary organic C source fuelling the microbial perturbation was glycerol released from the polymeric gel filling the reference electrodes (1.6 g glycerol/electrode). Other sources, such as acetone, may also have contributed to microbial processes, but only to a minor extent.     

Biogeochemical redox cycling of arsenic in mine-impacted lake sediments and co-existing pore waters near Giant Mine,Yellowknife Bay,Canada

Lacustrine sediments, submerged tailings, and their pore waters have been collected at several sites in Yellowknife Bay, Great Slave Lake, Canada, in order to investigate the biogeochemical controls on the remobilization of As from mining-impacted materials under different depositional conditions. Radiometric dating confirms that a mid-core enrichment of Pb, Zn, Cu and Sb corresponds to the opening of a large Au mine 60 a ago. This was evident even in a relatively remote site. Arsenic was enriched at mid-core, coincident with mining activity, but clearly exhibited post-depositional mobility, migrating upwards towards the sediment water interface (SWI) as well as down-core. Deep-water (15 m) Yellowknife Bay sediments that contain buried mine waste are suboxic, relatively organic-rich and abundant in microbes with As in pore waters and sediments reaching 585 μg/L and 1310 mg/kg, respectively. Late summer pore waters show equal proportions of As(III) and As(V) (16–415 μg/L) whereas late winter pore waters are dominated by As(III) (284–947 μg/L). This can be explained by As(III) desorption mechanisms associated with the conversion of FeS to FeS₂ and the reduction of As(V) to As(III) through the oxidation of dissolved sulfide, both microbially-mediated processes. Processes affecting As cycling involve the attenuating efficiency of the oxic zone at the SWI, sediment redox heterogeneity and the reductive dissolution of Fe(hydr)oxides by labile organic matter, temporarily and spatially variable.