Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments

The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH₂S and presence or absence of FeS_(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH₂S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS_(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH₂S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.     

Bio‐based Ester Oils for Use as Lubricants in Metal Working

The potential application of bio‐based ester oils for use as lubricants in metal working has been investigated for sustainable production processes in the future. When waste edible and animal fats came into focus as starting materials, it was already proven, that ester oils produced from plant fats performed very well as cooling lubricants. Waste fats were first characterized by analyzing and monitoring samples for one complete year. Inorganic and organic contaminations were found to be low and without seasonal variations. Fatty acid methyl esters (FAME) were produced by transesterification of the waste fats and they were separated into fractions with saturated FAME or unsaturated FAME by fractional crystallisation (winterisation). Further transesterification with 2‐ethylhexanol led to products that could be successfully tested as lubricants. The development of an extraction process aimed at the recycling of oil containing grinding mud by enabling the recirculation of lubricating oil and reutilization of oil‐free metal chips.     

Trace metals in acid sediments and waters, Pimpama catchment, southeast Queensland, Australia

The Pimpama River floodplain has developed over the last several thousand years as a result of sea-level fluctuations that shaped the lower catchment and enabled the formation of sedimentary pyrite. The subsequent production of sulfuric acid due to the oxidation of this pyrite enhances the breakdown of metal-bearing sediments and can lead to leaching of major and trace metals into the waters of the region. The seasonal pattern of rainfall and current land-use activities are important aspects that intensify the natural production of acid and influence the release and distribution of metals. To identify the source and migration of metals in the Pimpama catchment and to understand the impact of pyrite oxidation on the distribution of metals in sediments and waters, several components of the drainage system were analyzed: bedrock, sediments from river bed and bank, and water. The elements analyzed in this study (V, Cr, Co, Ni, Cu, Zn and Pb) are all present in the bedrock material which explains their occurrence in the unconsolidated sediments of the floodplain. These metals concentrate in the upper section of the sedimentary sequence and their presence is related to clay minerals such as smectite, organic matter and iron phases. However, Zn, Mo and Co occur in higher amounts than the local background and within standard shale. This comparison suggests that the diagenetic processes alone cannot explain the higher concentrations and it is concluded that these metals also have an anthropogenic source. The formation of sulfuric acid creates conditions for higher mobility of some metals, such as Cr, Co, Ni, Cu, Zn, but does not affect less mobile ones such as Mo and Pb. Over the longterm, the production of acid influences the breakdown of mineral phases and enhances the process of weathering. Over the short term, every rain event leaches acid from sediments and mobilizes metals resulting in a substantial reduction in the quality of river water. Received: 2 October 1998 · Accepted: 16 February 1999     

Yearly changes in the seasonal frequency and duration of short-term acid pulses in some Nova Scotia, Canada streams

 The seasonal frequency and duration of low pH events at three sites located in southwestern Nova Scotia were analyzed using measured and synthetic daily pH data. The basins varied in size from 0.3 to 300 km² and were subject to frequent snowmelt events in winter and spring, as well as occasional runoff events during summer and fall. Results showed that, in order to fill in missing data from periods where collection was interrupted, statistical approximations using discharge were not totally acceptable, as generated data consistently missed the extreme values measured. Despite a lack of totally accurate event pH estimates for periods where daily data were missing, analysis showed that in this region, low pH episodes can occur year-round including summer. The highest probabilities of low pH episodes nevertheless occurred in the winter and spring when snowmelts were frequent. Received: 12 November 1999 · Accepted: 18 July 2000     

Controls on the nature and distribution of an alga in coal mine-waste environments and its potential impact on water quality

 A dominant non-bacterial microorganism that may strongly impact environmental conditions in acid mine drainage at several Indiana coal mine sites is a single-celled protozoan, Euglena mutabilis. Field data suggest E. mutabilis has high tolerance for elevated total dissolved solids (TDS), to 18 g/l, and acid conditions to pH 1.7. Distribution is restricted to unmixed effluent pH<4.6, with prolific growth between pH 3.0 and 3.5. Additional factors influencing E. mutabilis include preference for areas with lower mineral/colloidal precipitation rates and a stable substrate of iron-rich precipitates. Initial studies indicate that in areas of prolific growth it contributes to oversaturation of dissolved oxygen by up to 200%. The presence of small orange intracellular crystalline-like structures, similar in color to iron oxyhydroxides, suggests that E. mutabilis may be sequestering iron, and possibly other metals. Further work is needed to determine if E. mutabilis contributes to natural mitigation of poor water quality at these and other coal mine sites. Received: 13 January 2000 · Accepted: 2 May 2000     

Partitioning of heavy metals on soil samples from column tests

In this study, column tests were used to determine the retention capability of three types of estuarine alluvia collected adjacent to landfill sites in South Wales. Selective sequential extraction (SSE) was used to study the retention mechanisms of heavy metals in the soil columns obtained from leaching experiments. Acid digestion was later used to check the validity of the SSE results. Breakthrough curves show good retention of heavy metal ions (Pb, Cu, and Zn) by all soils, where almost 99% of heavy metals were retained with the C_e/C_o values in the order of 10⁻³. The retention strength of these soils was observed to be constant up to five pore volumes (PV). This corresponds with the pH of the effluents and pore water of soil slices, which also show good buffering capacity against very acidic leachate up to 5PV. The heavy metal extraction profiles from SSE show very similar trends with the retention profiles from the leaching experiments, where heavy metals were retained mainly at the top part where the leachate entered the column. SSE indicates qualitatively that heavy metals precipitated with carbonates and amorphous materials (oxides/hydroxides) are higher than heavy metal retention via exchangeable mechanisms. The mass balance calculation gives range of deviation of 1–16% of the total soil extraction. The distribution of the heavy metals with various soil constituents are ranked in the following order: Carbonates>Amorphous oxides hydroxides>Organic matter>Exchangeable phases.     

滇黔桂卡林型金矿区水系沉积物和岩石金含量与时空分布

为研究滇黔桂卡林型金矿区水系沉积物和岩石中金的地球化学时空分布及其与金矿规模的对应关系,系统收集了该区1:20万区域化探全国扫面计划水系沉积物和全国地球化学基准计划岩石金的地球化学数据,绘制了水系沉积物和岩石金的地球化学分布图。滇黔桂卡林型金矿区以水系沉积物金地球化学异常面积大于1000 km^2为准,共圈定5处金的地球化学省,这些金的地球化学省同时也是矿床大规模产出的部位。区内右江盆地水系沉积物金背景值(1.94×10^–9)高于扬子克拉通(1.68×10^9),其内以泥岩、页岩、砂岩、灰岩为代表的容矿岩石金背景值(0.51×10^–9)也高于扬子克拉通(0.39×10^–9)。研究区不同构造单元及沉积相中水系沉积物金背景值受岩石金背景值的制约。金的地球化学省是地壳演化过程中不均匀分布的高金背景岩石、金矿化作用及金矿床次生风化作用相互叠加的结果。该研究有助于有效判断异常成因、识别成矿作用存在,对研究金的区域成矿规律和聚焦找矿靶区具有重要意义。     

Direct Observations of Atmospheric Transport and Stratosphere-Troposphere Exchange from High-Precision Carbon Dioxide and Carbon Monoxide Profile Measurements

The balloon-borne Aircore campaign was conducted in Inner Mongolia,China,on June 13 and 14 2018,which detected carbon dioxide(CO_2) and carbon monoxide(CO) profiles from surface to 24 km,showing strong positive and negative correlations between 8 km and 10 km on 13 and 14 June,respectively.Backward trajectories,meteorological analyses,and CO_2 horizontal distributions were combined to interpret this phenomenon.The results indicated that the source region experienced a stratospheric intrusion and exhibited a large horizontal CO_2 gradient;namely,lower CO concentrations corresponded to higher CO_2 concentrations and vice versa.The laminar structure with multiple origins resulted in the highly negative correlation between CO_2 and CO in the upper troposphere on 14 June.The contribution of stratospheric air mass to the upper troposphere and that of tropospheric air mass to the lower stratosphere were 26.7% and24.3%,respectively,based on a mass balance approach.Another interesting phenomenon is that CO_2 and CO concentrations increased substantially at approximately 8 km on 13 June.An analysis based on the backward trajectory implied that the air mass possibly came from anthropogenic sources.The slope of CO_2/CO representing the anthropogenic sources was 87.3 ppm ppm~(-1).In addition,the CO_2 profile showed that there was a large CO_2 gradient of 4 ppm km-1 within the boundary layer on 13 June,and this gradient disappeared on 14 June.     

Soil water dye tracing,with special reference to the use of rhodamine WT,lissamine FF and amino G acid

Three fluorescent dyes (Rhodamine WT, Lissamine FF and Amino G Acid) are compared for use in soil water tracing. Severe limitations are evident, but practical applications are possible. Background fluorescence, adsorption, desorption, pH and other non-adsorptive effects are reviewed in the contexts of soil column work and field tracing of soil water. Lissamine FF and Amino G Acid are to be preferred for soil column work because of their lower adsorption; Rhodamine WT exhibits higher adsorption but is useful in field situations where organic fluorescence backgrounds are high. Semi-quantitative work may be undertaken in soil columns once a priming and flushing procedure has been adopted.     

Weathering of sulfidic shale and copper mine waste: secondary minerals and metal cycling in Great Smoky Mountains National Park,Tennessee, and North Carolina,USA

Metal cycling via physical and chemical weathering of discrete sources (copper mines) and regional (non-point) sources (sulfide-rich shale) is evaluated by examining the mineralogy and chemistry of weathering products in Great Smoky Mountains National Park, Tennessee, and North Carolina, USA. The elements in copper mine waste, secondary minerals, stream sediments, and waters that are most likely to have negative impacts on aquatic ecosystems are aluminum, copper, zinc, and arsenic because these elements locally exceed toxicity guidelines for surface waters or for stream sediments. Acid-mine drainage has not developed in streams draining inactive copper mines. Acid-rock drainage and chemical weathering processes that accompany debris flows or human disturbances of sulfidic rocks are comparable to processes that develop acid-mine drainage elsewhere. Despite the high rainfall in the mountain range, sheltered areas and intermittent dry spells provide local venues for development of secondary weathering products that can impact aquatic ecosystems.Electronic Supplementary Material  Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.