Techniques for the Determination of Cyanide in a Process Environment: A Review

The determination of cyanide in various forms is important for industrial processes as well as for environmental investigations and monitoring associated with these processes. The accurate determination of cyanide is difficult for various reasons. Depending on the pH of the solution, cyanide is present both in molecular form (HCN) and ionic form (CN). Furthermore, cyanide is a good complexing reagent and reacts with almost all cations resulting in complexes with widely varying properties, such as stabilities, solubilities and rates of reaction. Cyanide also breaks down in sunlight and air, so that sampling and sample treatment become very important aspects to consider in the methodologies. During the last fifty years the determination of cyanide has been approached from various angles and a myriad of methods has been developed for its determination. This study represents a survey of methods commonly used in industrial laboratories for the analysis of cyanide-containing solutions. An overview of the nomenclature often used for the various forms of cyanides is discussed and the values resulting from a particular analysis will be interpreted. Most common interferences in samples originating from gold processing plants will be discussed.     

The implementation of an ecosystem approach to management within a federal government agency

This study examined how the United States’ National Oceanic and Atmospheric Administration (NOAA) has begun to implement and change its management strategy towards one of an ecosystem approach to management (EAM). In 2005, surveys were conducted with NOAA scientists and resource managers in nine NOAA programs in eight geographic regions across the United States. We quantitatively examined temporal and spatial trends in NOAA's EAM project implementation. Through a qualitative analysis of the data, we identified important lessons learned, best practices, and challenges of NOAA EAM projects. A content analysis identified three of the most frequently provided “success strategies” and include: (1) encouraging collaborations, (2) utilizing multidisciplinary approaches, and (3) identifying common priorities among constituents. We conclude with recommendations for initiatives that NOAA, and others interested in EAM, can undertake to facilitate further ecosystem management opportunities.     

Direct bed shear stress measurements in bore-driven swash

Direct measurements of bed shear in the swash zone are presented. The data were obtained using a shear plate in medium and large-scale laboratory bore-driven swash and cover a wide range of bed roughness. Data were obtained across the full width of the swash zone and are contrasted with data from the inner surf zone. Estimates of the flow velocities through the full swash cycle were obtained through numerical modelling and calibrated against measured velocity data. The measured stresses and calculated flow velocities were subsequently used to back-calculate instantaneous local skin friction coefficients using the quadratic drag law. The data show rapid temporal variation of the bed shear stress through the leading edge of the uprush, which is typically two–four times greater than the backwash shear stresses at corresponding flow velocity. The measurements indicate strong temporal variation in the skin friction coefficient, particularly in the backwash. The general behaviour of the skin friction coefficient with Reynolds number is consistent with classical theory for certain stages of the swash cycle. A spatial variation in skin friction coefficient is also identified, which is greatest across the surf-swash boundary and likely related to variations in local turbulent intensities. Skin friction coefficients during the uprush are approximately twice those in the backwash at corresponding Reynolds number and cross-shore location. It is suggested that this is a result of the no-slip condition at the tip leading to a continually developing leading edge and boundary layer, into which high velocity fluid and momentum are constantly injected from the flow behind and above the tip region. Finally, the measured stress data are used to determine the asymmetry and cross-shore variation in potential sediment transport predicted by three forms of sediment transport formulae.     

Detecting inhomogeneity in daily climate series using wavelet analysis

A wavelet method was applied to detect inhomogeneities in daily meteorological series, data which are being increasingly applied in studies of climate extremes. The wavelet method has been applied to a few well- established long-term daily temperature series back to the 18th century, which have been ＂homogenized＂ with conventional approaches. Various types of problems remaining in the series were revealed with the wavelet method. Their influences on analyses of change in climate extremes are discussed. The results have importance for understanding issues in conventional climate data processing and for development of improved methods of homogenization in order to improve analysis of climate extremes based on daily data.     

An overview of MODIS radiometric calibration and characterization

The Moderate Resolution Imaging Spectroradiometer (MODIS) is one of the key instruments for NASA’s Earth Observing System (EOS), currently operating on both the Terra and Aqua satellites. The MODIS is a major advance over the previous generation of sensors in terms of its spectral, spatial, and temporal resolutions. It has 36 spectral bands: 20 reflective solar bands (RSB) with center wavelengths from 0.41 to 2.1 μm and 16 thermal emissive bands (TEB) with center wavelengths from 3.7 to 14.4 μm, making observations at three spatial resolutions: 250 m (bands 1–2), 500 m (bands 3–7), and 1km (bands 8-36). MODIS is a cross-track scanning radiometer with a wide field-of-view, providing a complete global coverage of the Earth in less than 2 days. Both Terra and Aqua MODIS went through extensive pre-launch calibration and characterization at various levels. In orbit, the calibration and characterization tasks are performed using its on-board calibrators (OBCs) that include a solar diffuser (SD) and a solar diffuser stability monitor (SDSM), a v-grooved flat panel blackbody (BB), and a spectro-radiometric calibration assembly (SRCA). In this paper, we present an overview of MODIS calibration and characterization activities, methodologies, and lessons learned from pre-launch characterization and in-orbit operation. Key issues discussed in this paper include in-orbit efforts of monitoring the noise characteristics of the detectors, tracking the solar diffuser and optics degradations, and updating the sensor’s response versus scan angle. The experiences and lessons learned through MODIS have played and will continue to play major roles in the design and characterization of future sensors.     

Did the massive magnetite “lava flows” of El Laco (Chile) form by magmatic or hydrothermal processes? New constraints from magnetite composition by LA-ICP-MS

The El Laco magnetite deposits consist of more than 98 % magnetite but show field textures remarkably similar to mafic lava flows. Therefore, it has long been suggested that they represent a rare example of an effusive Fe oxide liquid. Field and petrographic evidence, however, suggest that the magnetite deposits represent replacement of andesite flows and that the textures are pseudomorphs. We determined the trace element content of magnetite by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) from various settings at El Laco and compared them with magnetite from both igneous and hydrothermal environments. This new technique allows us to place constraints on the conditions under which magnetite in these supposed magnetite “lava flows” formed. The trace element content of magnetite from the massive magnetite samples is different to any known magmatic magnetite, including primary magnetite phenocrysts from the unaltered andesite host rocks at El Laco. Instead, the El Laco magnetite is most similar in composition to hydrothermal magnetite from high-temperature environments (>500 °C), such as iron oxide-copper-gold (IOCG) and porphyry-Cu deposits. The magnetite trace elements from massive magnetite are characterised by (1) depletion in elements considered relatively immobile in hydrothermal fluids (e.g. Ti, Al, Cr, Zr, Hf and Sc); (2) enrichment in elements that are highly incompatible with magmatic magnetite (rare earth elements (REE), Si, Ca, Na and P) and normally present in very low abundance in magmatic magnetite; (3) high Ni/Cr ratios which are typical of magnetite from hydrothermal environments; and (4) oscillatory zoning of Si, Ca, Mg, REE and most high field strength elements, and zoning truncations indicating dissolution, similar to that formed in hydrothermal Fe skarn deposits. In addition, secondary magnetite in altered, brecciated host rock, forming disseminations and veins, has the same composition as magnetite from the massive lenses. Euhedral magnetite lining both open-spaced veins in the brecciated host rock and along the walls of large, hollow chimneys in the massive magnetite lenses also displays oscillatory zoning and most likely formed by fluctuating composition and/or physio-chemical conditions of the fluid. Thus, the chemical fingerprint of magnetite from the supposed El Laco magnetite lava flows supports the hydrothermal model of metasomatic replacement of andesite lava flows, by dissolution and precipitation of magnetite from high-temperature fluids, rather than a magmatic origin from an effusive Fe oxide liquid.     

Time scales and length scales in magma flow pathways and the origin of magmatic Ni–Cu–PGE ore deposits

Ore forming processes involve the redistribution of heat, mass and momentum by a wide range of processes operating at different time and length scales. The fastest process at any given length scale tends to be the dominant control. Applying this principle to the array of physical processes that operate within magma flow pathways leads to some key insights into the origins of magmatic Ni–Cu–PGE sulfide ore deposits. A high proportion of mineralised systems, including those in the super-giant Noril'sk-Talnakh camp, are formed in small conduit intrusions where assimilation of country rock has played a major role. Evidence of this process is reflected in the common association of sulfides with vari-textured contaminated host rocks containing xenoliths in varying stages of assimilation. Direct incorporation of S-bearing country rock xenoliths is likely to be the dominant mechanism for generating sulfide liquids in this setting. However, the processes of melting or dissolving these xenoliths is relatively slow compared with magma flow rates and, depending on xenolith lithology and the composition of the carrier magma, slow compared with settling and accumulation rates. Chemical equilibration between sulfide droplets and silicate magma is slower still, as is the process of dissolving sulfide liquid into initially undersaturated silicate magmas. Much of the transport and deposition of sulfide in the carrier magmas may occur while sulfide is still incorporated in the xenoliths, accounting for the common association of magmatic sulfide-matrix ore breccias and contaminated “taxitic” host rocks. Effective upgrading of so-formed sulfide liquids would require repetitive recycling by processes such as re-entrainment, back flow or gravity flow operating over the lifetime of the magma transport system as a whole. In contrast to mafic-hosted systems, komatiite-hosted ores only rarely show an association with externally-derived xenoliths, an observation which is partially due to the predominant formation of ores in lava flows rather than deep-seated intrusions, but also to the much shorter timescales of key component systems in hotter, less viscous magmas. Nonetheless, multiple cycles of deposition and entrainment are necessary to account for the metal contents of komatiite-hosted sulfides. More generally, the time and length scale approach introduced here may be of value in understanding other igneous processes as well as non-magmatic mineral systems.     

Further-Adjusted Long-Term Temperature Series in China Based on MASH

A set of homogenized monthly mean surface air temperature(SAT) series at 32 stations in China back to the 19 th century had previously been developed based on the RHtest method by Cao et al.,but some inhomogeneities remained in the dataset.The present study produces a further-adjusted and updated dataset based on the Multiple Analysis of Series for Homogenization(MASH) method.The MASH procedure detects 33 monthly temperature records as erroneous outliers and152 meaningful break points in the monthly SAT series since 1924 at 28 stations.The inhomogeneous parts are then adjusted relative to the latest homogeneous part of the series.The new data show significant warming trends during 1924–2016 at all the stations,ranging from 0.48 to 3.57?C(100 yr)~(-1),with a regional mean trend of 1.65?C(100 yr)~(-1);whereas,the previous results ranged from a slight cooling at two stations to considerable warming,up to 4.5?C(100 yr)~(-1).It is suggested that the further-adjusted data are a better representation of the large-scale pattern of climate change in the region for the past century.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

观测序列的不均一性对估算北京和上海的平均温度与极端温度变化趋势的影响

根据北京和上海气象观测站的详细历史资料，修正了两站逐日温度序列的不均一性，并分析这种不均一性对长期气候变化趋势估计的影响。对北京序列，不同时期的主要修正幅度在－０．３３－０．６℃；对上海序列则为－０．３３－０．３℃。从逐日序列计算出年平均温度和年极端温度序列，并把修正之前和修正之后的序列趋势进行比较，修正之后的两站年平均温度序列自２０世纪初起呈现出０．５℃／百年的变暖趋势，自２０世纪６０年代起这一趋势增强为２．０℃／百年。相比之下，上海的未修正资料显示出两倍于此的趋势；北京的未修正资料几乎没有长期趋势，而对近期的变暖趋势则高估了５０％－３０％。北京温度序列在２０世纪４０年代至７０年代呈变冷趋势，极端事件的频率降低；此后又呈变暖趋势，极端事件的频率增加。上海温度极端事件的变化趋势基本呈相反趋。这意味着即使区域性平均温度变化一致，区域性强天气波动的变化趋势也会有所不同。