Chemical characterization and sources of PM2.5 at 12-h resolution in Guiyang,China

The increasing emission of primary and gaseous precursors of secondarily formed atmospheric particulate matter due to continuing industrial development and urbanization are leading to an increased public awareness of environmental issues and human health risks in China. As part of a pilot study, 12-h integrated fine fraction particulate matter (PM_2.5) filter samples were collected to chemically characterize and investigate the sources of ambient particulate matter in Guiyang City, Guizhou Province, southwestern China. Results showed that the 12-h integrated PM_2.5 concentrations exhibited a daytime average of 51 ± 22 µg m^?3 (mean ± standard deviation) with a range of 17–128 µg m^?3 and a nighttime average of 55 ± 32 µg m^?3 with a range of 4–186 µg m^?3. The 24-h integrated PM_2.5 concentrations varied from 15 to 157 µg m^?3, with a mean value of 53 ± 25 µg m^?3, which exceeded the 24-h PM_2.5 standard of 35 µg m^?3 set by USEPA, but was below the standard of 75 µg m^?3, set by China Ministry of Environmental Protection. Energy-dispersive X-ray fluorescence spectrometry (XRF) was applied to determine PM_2.5 chemical element concentrations. The order of concentrations of heavy metals in PM_2.5 were iron (Fe) > zinc (Zn) > manganese (Mn) > lead (Pb) > arsenic (As) > chromium (Cr). The total concentration of 18 chemical elements was 13 ± 2 µg m^?3, accounting for 25% in PM_2.5, which is comparable to other major cities in China, but much higher than cities outside of China.     

Assessment of environmental impact of open burning of scrap tyres on ambient air quality

Open burning of scrap (bicycle, motorcycle, car and truck) tyres (OBST) was simulated in the laboratory to investigate their impact on the ambient air quality. The tyre samples were burnt in combustion chamber, and gaseous pollutants (CO, NO₂ and SO₂) emitted were quantified, while concentrations and elemental compositions of emitted total suspended particulates (TSP) were determined. Emission level of SO₂ from all the tyre samples exceeded USEPA allowable (156.74 µg/m³) limit. CO due to car and truck tyres exceeded USEPA allowable (10,285.71 µg/m³) limit, while NO₂ concentration was below the allowable limit (56.33 µg/m³) only in bicycle tyre. 25% of all the gaseous pollutants emitted are within the Air Quality Index range of 101–150. TSP concentrations from all the tyre samples were higher than the Federal Ministry of Environment standard (250 µg/m³) for ambient TSP. There is strong correlation (R) of 0.885, 0.949 and 0.802 among all the gaseous (CO/NO₂, CO/SO₂ and NO₂/SO₂) pollutants, respectively, while the highest (0.999) and lowest (0.079) positive correlations were observed between Mg and Mn as well as Cd and Zn, respectively. The results of this study show that OBST emits hazardous pollutants, which pose serious threat to human health and environment.     

大气干湿沉降: 地下河多环芳烃的重要来源——以广西清水泉地下河为例

为证实大气干湿沉降物是岩溶地下河中多环芳烃(PAHs)的来源,研究选择了某城市典型的岩溶地下河水源地作为研究地点,采用大气干湿采样器、聚氨酯泡沫(PUF)大气被动采样器分别采集大气及其干湿沉降物样品,同时采集地下河水样和分层采集流域土壤,利用气相色谱-质谱联用仪(GC-MS)测定了16种PAHs优先控制污染物。结果表明,地下河流域大气干湿沉降中PAHs的干湿沉降通量为147.26 ng·(m2·d)-1,流域PAHs沉降量为1943.8 g;大气中的PAHs浓度为45.33 ng·m-3;地下河水中PAHs浓度平均值为220.98 ng·L-1;土壤中PAHs浓度为38.72 ng·g-1;大气、降雨和土壤中PAHs组成以2~3环的萘、芴、菲、荧蒽、芘5种为主,地下河水中以芴、菲、荧蒽、芘、苯并[a]蒽、苯并[a]芘6种为主。利用地下河多介质中的16种PAHs成分谱、特征比值结合它们的物理化学性质进行PAHs的源解析,研究显示大气干湿沉降是岩溶地下河水中多环芳烃的主要污染源之一,这归因于岩溶地区防污性能的脆弱性。     

Wood chips as soil conservation in field conditions

The soil conditioner in processes of soil conservation is important especially in heavily eroded areas. Because in this study done in Educational and Research Forest Watershed of Tarbiat Modares University, north of Iran, the experiments created four treatments of control and different wood chips with rates of 0.5, 1, and 1.5 kg m^?2, by rainfall simulation in rainfall intensity of 60 mm h^?1, and plot scale of 1 m² on changing ponding time, runoff coefficient, sediment concentration, and soil loss. The results showed that the average change ponding time in control treatment and wood chip treatments with rates of 0.5, 1, and 1.5 kg m^?2 were 4.25, 7.48, 11.63, and 12.45 min. Also, the average change runoff coefficient in control treatment and wood chip treatments with rates of 0.5, 1, and 1.5 kg m^?2 were 50.03, 26.27, 15.28, and 13.17 %. The results also indicated that the wood chips could decrease average soil loss with the rates of ?52.15, ?82.18, and ?89.35 % compared with control treatment for 0.5, 1, and 1.5 kg m^?2 of wood chips, respectively. The one-way ANOVA results showed that the runoff coefficient, sediment concentration, and soil loss decreased with increasing wood chip amount, and the effect of conservation treatment was significant on study variables (R ² = 0.99). But, the ponding time increased with increasing wood chip amount, and this effect was significant on study variables (R ² = 0.99).     

Crystal nucleation and growth produced by continuous decompression of Pinatubo magma

High-temperature decompression experiments demonstrate that crystal textures preserve a record of the style and rate of magmatic ascent. To reinforce this link, we performed a suite of isothermal decompression experiments using starting material from the climactic 1991 Pinatubo eruption. We decompressed experiments from 220 MPa to final, quench pressures of 75 or 30 MPa using continuous decompression rates of 100, 30, 10, 3, 1, and 0.3 MPa h^?1. Amphibole, clinopyroxene, and plagioclase crystallized during the experiments, with plagioclase microlites dominating the assemblage. Total microlite number densities range from 10^7.6±0.4 up to 10^8.2±0.2 cm^?3, with plagioclase accounting for up to 65% of the total number. Plagioclase microlite area increased systematically from 19?±?8 to 937?±?487 µm² with increasing experiment duration. Our textures provide time-integrated records of crystal kinetics. Average nucleation and areal growth rates of plagioclase are highest in the fastest decompressions (~?10^7.5 cm^?3 h^?1 and 10.1?±?4.1 µm² h^?1, respectively) and more than an order of magnitude lower in the slowest experiments (~?10^5.5 cm^?3 h^?1 and 0.8?±?0.2 µm² h^?1, respectively). Both nucleation and growth rates are highest at high degrees of disequilibrium. We find that peak supersaturation-dependent instantaneous rates are generally more than an order of magnitude faster than average rates. We use those instantaneous nucleation and growth rates to introduce an iterative model to evaluate the effects of different decompression rates, decompression paths (continuous, single-step or multistep), and the presence of phenocrysts on final crystallinity and microlite size distribution.     

The effects of Typhoon Morakot on concentration of airborne particulates derived from unvegetated riverbanks

Landslides frequently occur during large earthquakes and storms in Taiwan, supplying large volumes of sediment to downslope areas. When coupled with the intense northeast monsoon over Taiwan in the dry winter season, this can lead to high concentrations of airborne particulates that are hazardous to human health. Air quality monitoring stations near unvegetated riverbanks recorded high concentrations of particulate matter less than 10 μm (PM₁₀) after Typhoon Morakot in 2009. The objective of this study was, therefore, to analyze the effects on air quality of sediment caused by the typhoon. A deflation module was simulated, and the resulting estimates were compared with observed data from the Taitung monitoring station for 2004 and 2005. The relationship of dust flux to average atmospheric dust concentration was analyzed for October to December 2001–2010. Analysis showed that the 2001–2008 data are highly correlated (0.78) with the average concentration. The intercept of 28.07 represented the background concentration with no dust emission, from October to December of 2001–2008. Based on the dust flux potential in 2009, the average yearly PM₁₀ concentration would be 37.98 µg/m³; however, the measured concentration was 61.67 µg/m³ from October to December. This suggests the strong influence of dust re-suspended from unvegetated riverbanks by Typhoon Morakot.     

Loading, Transformation, and Retention of Nitrogen and Phosphorus in the Tidal Freshwater James River (Virginia)

A nutrient mass balance for the tidal freshwater segment of the James River was used to assess sources of nutrients supporting phytoplankton production and the importance of the tidal freshwater zone in mitigating nutrient transport to marine waters. Monthly mass balances for 2007–2010 were based on riverine inputs, local point sources (including sewer overflow events), ungauged inputs, riverine outputs, and tidal exchange. The tidal freshwater James River received exceptionally high areal loads (446 mg TN m^?2 day^?1 and 55 mg TP m^?2 day^?1) compared to other estuaries in the region and elsewhere. P inputs were principally from riverine sources (84 %) whereas point sources contributed appreciably (54 %) to high N loads. Despite high loading rates and short water residence time, areal mass retention was high (143 mg TN m^?2 day^?1 and 33 mg TP m^?2 day^?1). Retention of particulate fractions occurred during high discharge, whereas dissolved inorganic fractions were retained during low discharge when chlorophyll-a concentrations were high. On an annualized basis, P was retained more effectively (59 %) than N (32 %). P was retained by abiotic mechanisms via trapping of particulate forms, whereas N was retained through biological assimilation of dissolved inorganic forms. Results from a limited suite of stable isotope determinations suggest that DIN from point sources was preferentially retained. Combined inputs from diffuse and point sources accounted for only 20 % and 36 % (respectively) of estimated algal N and P demand, indicating that internal nutrient recycling was important to sustaining high rates of phytoplankton production in the tidal freshwater zone.     

Comparisons of annual ambient air pollutant concentrations and dry deposition flux variations for day and nighttime in middle Taiwan

This study monitored ambient air particles and the metallic elements Cu, Cr, Cd, Pb, and Zn in total suspended particulate (TSP) concentrations and dry deposition during the day and nighttime sampling period at a traffic sampling site in central Taiwan from 2012 March to 2013 February. The dry deposition flux ratios and seasonal concentration variations of ambient air particles and these metallic elements are also discussed. The results indicate that for all the elements, except for Zn, the highest average concentrations in TSP occurred in the spring and summer, while the lowest average was in the fall and winter for both day and nighttime sampling periods.     

Isolation and characterization of metal-resistant bacterial strain from wastewater and evaluation of its capacity in metal-ions removal using living and dry bacterial cells

A novel strain of the genus Micrococcus isolated from wastewater was studied for resistance to seven heavy metals and forty antibiotics. Its capacity to accumulate metal ions was also realized at different pH. The strain exhibited high minimal inhibitory concentration values for metal ions tested and resist to 15 antibiotics. The living cells of the bacterial strain show a largest uptake capacity at pH 6–8.5 for copper, nickel, and zinc with values ranging from 51.45 to 83.90 %, 52.59 to 78.81 %, and 59.55 to 78.90 %, respectively. It was also able to absorbed 59.81–80.08 % of chromium and 58.09–79.41 % of cobalt at pH 7.3–8.5. The maximum lead uptake was obtained at pH 5.5–8.5 with an amount of 55.28–91.06 %. The significant absorption of cadmium was shown at pH 6.5 with 38 %. In 25 µg mL-1 zinc, chromium, and nickel solutions, dead cells of the isolate were able to biosorbed 20.46, 22.5, and 23.98 µg mL^?1, respectively, after 30 min of contact. In other solutions with higher concentrations 50 and 100 µg mL^?1, the amount of each metal immobilized was, respectively, as follows: 38.02 and 90.21 µg mL^?1 for zinc, 39.78 and 89.23 µg mL^?1 for chromium, and 47.19 and 86.83 µg mL^?1 for nickel. Due to its high-metal accumulation capacity in aerobic conditions, these Gram-positive bacteria may be potentially applicable in situ bioremediation of heavy metals contaminating aqueous systems.     

Relationships Between Settlements of Circular and Square Bearing Plates/Footings and Deformation Zones Developing Beneath Them

ASTM Standards instruct experimenters to use circular or square bearing plates/footings having areas ranging between 0.073 and 0.456 m². In general, researchers and contractors perform loading bearing plate/footing tests using plates/footings which have dimensions exceeding the ones recommended by the Standards. This paper offers formulas describing relationships between settlements of square and circular plates/footings having areas ranging between 0.5 and 4.0 m² and deformation zones developing beneath them. The proposed formulas are verified by the results of field tests performed with circular and square plates or footings supported by cohesive soils.     

Influence of car body repair activities on particulate matter pollution in a suburban area (Bouzaréah City,Algiers)

This work was carried out in order to study the impact of car body repair activities in Bouzaréah City (suburban area located at the plateau of Algiers) on the air quality. Atmospheric particulate matter was targeted using high-volume sampler. Precisely, the particulate organic matter such as organophosphate esters, especially triphenyl phosphate and tributyl phosphate, was evaluated by the implementation of accelerated solvent extraction. The results of the major extractable organic components revealed that tributyl phosphate and triphenyl phosphate were found at 5.46 and 1.78 ng m^?3, respectively. On the other hand, the classical pollutants such as n-alkanes, n-alkanoic monocarboxylic acids and polycyclic aromatic hydrocarbons were also measured, respectively, at average total concentrations of 35.8, 107.4 and 9.8 ng m^?3. This work confirms that sanding and painting car bodies may contribute to air pollution, especially after detection of diethylnitrosamine which remains the most surprising compound in the particulate matter due to its volatility and can be considered as emerging contaminant.     

Decadal Change in Sediment Community Oxygen Consumption in the Abyssal Northeast Pacific

Long time-series studies are critical to assessing impacts of climate change on the marine carbon cycle. A 27-year time-series study in the abyssal northeast Pacific (Sta. M, 4000 m depth) has provided the first concurrent measurements of sinking particulate organic carbon supply (POC flux) and remineralization by the benthic community. Sediment community oxygen consumption (SCOC), an estimate of organic carbon remineralization, was measured in situ over daily to interannual periods with four different instruments. Daily averages of SCOC ranged from a low of 5.0 mg C m^?2 day^?1 in February 1991 to a high of 31.0 mg C m^?2 day^?1 in June 2012. POC flux estimated from sediment trap collections at 600 and 50 m above bottom ranged from 0.3 mg C m^?2 day^?1 in October 2013 to 32.0 mg C m^?2 day^?1 in June 2011. Monthly averages of SCOC and POC flux correlated significantly with no time lag. Over the long time series, yearly average POC flux accounted for 63 % of the estimated carbon demand of the benthic community. Long time-series studies of sediment community processes, particularly SCOC, have shown similar fluctuations with the flux of POC reaching the abyssal seafloor. SCOC quickly responds to changes in food supply and tracks POC flux. Yet, SCOC consistently exceeds POC flux as measured by sediment traps alone. The shortfall of ~37 % could be explained by sediment trap sampling artifacts over decadal scales including undersampling of large sinking particles. High-resolution measurements of SCOC are critical to developing a realistic carbon cycle model for the open ocean. Such input is essential to evaluate the impact of climate change on the oceanic carbon cycle, and the long-term influences on the sedimentation record.     

Development of low-cost passive sampler from cow bone char for sampling of volatile organic compounds

A simple and low-cost passive sampler for collection of volatile organic compounds, specifically benzene, toluene, ethylbenzene and xylene (BTEX), from the ambient air has been developed by using cow bone char (CBC) as an adsorbent with desorption by solvent extraction prior to analysis by gas chromatography–mass spectrometry (GC–MS). The laboratory-made CBC was prepared by calcination process in a partially oxidative atmosphere. The developed passive sampler was tested for a suitable amount of CBC used, diffusion tube type and size, and sampling duration, in a closed chamber saturated with each of the BTEX vapors. With the optimum amount of 250 mg CBC packed in a glass bottle (82.6 mm height × 11.1 mm i.d.) and the exposure time of 168 h, detection limits (µg/m³) for BTEX determination using this developed sampler together with GC–MS were 0.28 (benzene), 0.79 (toluene), 0.58 (ethylbenzene), 0.28 (p-xylene) and 0.54 (o-xylene). The proposed method was applied to sampling BTEX from selected petrol stations, traffic congestion areas and a rural area in Chiang Mai Province, Thailand. The BTEX concentrations detected were well correlated with their sources as they were the highest at the petrol station sites, lower at the traffic congestion area sites and the lowest at the rural area site. The laboratory-made passive sampler containing CBC has thus opened up a possibility of having a simple and effective device for sampling of BTEX in the ambient air.     

Experimental growth of åkermanite reaction rims between wollastonite and monticellite: evidence for volume diffusion control

Growth rates of monomineralic, polycrystalline åkermanite (Ca₂MgSi₂O₇) rims produced by solid-state reactions between monticellite (CaMgSiO₄) and wollastonite (CaSiO₃) single crystals were determined at 0.5 GPa dry argon pressure, 1,000–1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite–wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient \( D_{\text{eff,MgO}}^{\text{Ak}} \) is calculated to 10^?15.8±0.1 m² s^?1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E _a = 204 ± 18 kJ/mol and D ₀ = 10^?8.6±1.6 m² s^?1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect \( D_{\text{eff,MgO}}^{\text{Ak}} \) to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO–SiO₂ binary system, where grain boundary diffusion controls rim growth.     

Bedded jaspers of the Ordovician Løkken ophiolite,Norway: seafloor deposition and diagenetic maturation of hydrothermal plume-derived silica-iron gels

Sedimentary beds of jasper (red hematitic chert) in the Ordovician Løkken ophiolite of Norway are closely associated with volcanogenic massive sulphide (VMS) deposits. The jaspers occur in the immediate hangingwall and laterally peripheral to the large Løkken (25–30 Mt) and small Høydal (0.1 Mt) VMS deposits, and are exposed discontinuously for several kilometres along strike. Massive or laminated types predominate; jasper-sulphide debris-flow deposits are also abundant near VMS deposits. The jaspers contain hematite-rich laminae showing soft-sediment deformation structures and microtextural evidence that record the presence of a colloidal precursor and an origin as gels. Early textures include: (1) straight or curved chains of hematitic filaments 3–10 µm in diameter and 20–100 µm long; (2) branching networks of 15–25 µm-thick, tubular structures surrounded by cryptocrystalline hematite and filled with quartz and euhedral hematite; (3) small (up to 10 µm) spherules composed of cryptocrystalline hematite and silica; and (4) up to 50 µm silica spherules with hematitic cores. The small filaments seem to have been deposited in varying proportions in the primary laminae, possibly together with hematitic and siliceous microspheroids. Diagenetic changes are represented by polygonal syneresis cracks, and the presence of cryptocrystalline (originally opaline) silica, chalcedony, quartz, carbonate and cryptocrystalline hematite and/or goethite forming botryoidal masses and spheroids <10 µm to 5 mm in diameter. Coarser euhedral grains of quartz, carbonate, and hematite are integral parts of these textures. Bleached, silica-rich jaspers preserve only small relics of fine-grained hematite-rich domains, and locally contain sparse pockets composed of coarse euhedral hematite±epidote. The jaspers are interpreted to record colloidal fallout from one or more hydrothermal plumes, followed by maturation (ageing) of an Si-Fe-oxyhydroxide gel, on and beneath the Ordovician sea floor. Small hematitic filaments in the jaspers reflect bacteria-catalysed oxidation of Fe ²⁺ within the plume. The larger tubular filaments resulted from either microbial activity or inorganic self-organized mineral growth of Fe-oxyhydroxide within the Si-Fe-oxyhydroxide gel after deposition on the sea floor, prior to more advanced maturation of the gel as represented by the spheroidal and botryoidal silica-hematite textures. Bleaching and hematite±epidote growth are interpreted to reflect heat and fluids generated during deposition of basaltic sheet flows on top of the gels.     

Seasonal Oxygen Dynamics in a Warm Temperate Estuary: Effects of Hydrologic Variability on Measurements of Primary Production,Respiration, and Net Metabolism

Seasonal responses in estuarine metabolism (primary production, respiration, and net metabolism) were examined using two complementary approaches. Total ecosystem metabolism rates were calculated from dissolved oxygen time series using Odum’s open water method. Water column rates were calculated from oxygen-based bottle experiments. The study was conducted over a spring-summer season in the Pensacola Bay estuary at a shallow seagrass-dominated site and a deeper bare-bottomed site. Water column integrated gross production rates more than doubled (58.7 to 130.9 mmol O₂ m^?2 day^?1) from spring to summer, coinciding with a sharp increase in water column chlorophyll-a, and a decrease in surface salinity. As expected, ecosystem gross production rates were consistently higher than water column rates but showed a different spring-summer pattern, decreasing at the shoal site from 197 to 168 mmol O₂ m^?2 day^?1 and sharply increasing at the channel site from 93.4 to 197.4 mmol O₂ m^?2 day^?1. The consistency among approaches was evaluated by calculating residual metabolism rates (ecosystem ? water column). At the shoal site, residual gross production rates decreased from spring to summer from 176.8 to 99.1 mmol O₂ m^?2 day^?1 but were generally consistent with expectations for seagrass environments, indicating that the open water method captured both water column and benthic processes. However, at the channel site, where benthic production was strongly light-limited, residual gross production varied from 15.7 mmol O₂ m^?2 day^?1 in spring to 86.7 mmol O₂ m^?2 day^?1 in summer. The summer rates were much higher than could be realistically attributed to benthic processes and likely reflected a violation of the open water method due to water column stratification. While the use of sensors for estimating complex ecosystem processes holds promise for coastal monitoring programs, careful attention to the sampling design, and to the underlying assumptions of the methods, is critical for correctly interpreting the results. This study demonstrated how using a combination of approaches yielded a fuller understanding of the ecosystem response to hydrologic and seasonal variability.     

Soil radon in winter months under snowpack in Hokkaido, Japan

Soil radon (²²²Rn) has been monitored during winter months under cool-temperate deciduous stands of different surface geology in Tomakomai and in Sapporo, Hokkaido, Japan. Radon level was lower in Tomakomai of immature soil of porous volcanic ash emitted from an active volcano (Mt. Tarumae), compared with those in Sapporo of alluvial sediments. In Tomakomai, mean value of the ²²²Rn activity concentration was higher in winter (570 Bq m^?3) than in summer (350 Bq m^?3) at a depth of 1 m, which is consistent with the results in cold and dry winter reported in the literature. In contrast, soil radon decreasing with decreasing soil temperature from mid-September (5.0 kBq m^?3) remained low (2.6 kBq m^?3) under persistent snow in Sapporo, which had already been observed in the same location. Measurements of the activity concentrations of ²²²Rn in snow and in snow air as well as in soil air indicate that the small amount of ²²²Rn is released from the ground surface to the overlying snowpack with a ²²²Rn flux density of 0.4 mBq m^?2 s^?1 under thick snow cover in Sapporo.     

Groundwater,Acid and Carbon Dioxide Dynamics Along a Coastal Wetland,Lake and Estuary Continuum

Coastal wetlands are hotspots for biodiversity and biological productivity, yet the hydrology and carbon cycling within these systems remains poorly understood due to their complex nature. By using a novel spatiotemporal approach, this study quantified groundwater discharge and the related inputs of acidity and CO₂ along a continuum of a modified coastal acid sulphate soil (CASS) wetland, a coastal lake and an estuary under highly contrasting hydrological conditions. To increase the resolution of spatiotemporal data and advance upon previous methodologies, we relied on automated observations from four simultaneous time-series stations to develop multiple radon mass balance models to estimate groundwater discharge and related groundwater inputs of acidity and dissolved inorganic carbon (DIC), along with surface water to atmosphere CO₂ fluxes. Spatial surveys indicated distinct acid hotspots with minimum surface water pH of 2.91 (dry conditions) and 2.67 (flood conditions) near a non-remediated (drained) CASS area. Under flood conditions, groundwater discharge accounted for ～14.5 % of surface water entering the lake. During the same period, acid discharge from the acid sulphate soil section of the continuum produced ～4.8 kg H₂SO₄?ha^?1 day^?1, a rate much higher than previous studies in similar systems. During baseflow conditions, the low pH water was rapidly buffered within the estuarine lake, with the pH increasing from 4.22 to 6.07 over a distance of ～250 m. The CO₂ evasion rates within the CASS were extremely high, averaging 2163?±?125 mmol m^?2 day^?1 in the dry period and 4061?±?259 mmol m^?2 day^?1 under flood conditions. Groundwater input of DIC could only account for 0.4 % of this evasion in the dry conditions and ～5 % during the flood conditions. We demonstrated that by utilising a spatiotemporal (multiple time-series stations) approach, the study was able to isolate distinct zones of differing hydrology and biogeochemistry, whilst providing more reasonable groundwater acid input estimates and air–water CO₂ flux estimates than some traditional sampling designs. This study highlights the notion that modified CASS wetlands can release large amounts of CO₂ to the atmosphere because of high groundwater acid inputs and extremely low surface water pH.     

Studies on an efficient method for determining ethyl carbamate in the workplace air

In relation to the proposal to introduce an occupational exposure limit value for ethyl carbamate (EC) in Poland, a need to develop a sensitive method for determination of this carcinogenic substance in the workplace air was emerged. In the presented paper, a new method for its determination by high-performance liquid chromatography (HPLC) with fluorescence detector (FLD) is proposed. The method is based on the adsorption of EC on the cellulose filter, its extraction with water, further reaction of EC with 9-xanthydrol in acidic solution. Determination of the obtained EC derivative (N-xanthyl ethyl carbamate) was then conducted in a reverse-phase system with acetonitrile and water mobile phase at a flow rate of 1 mL/min on an Ultra C18 column of 250 mm by HPLC–FLD. Measurement range of 0.1–2 µg/m³ for a 1440 L of air sample was appropriate to the established maximum admissible concentration value of 1 µg/m³. The limit of detection is 0.142 ng/mL, and the limit of quantification is 0.426 ng/mL, respectively. The developed quantitative method makes it possible to determine ethyl carbamate in workplace air, which in turn allows determining exposure indicators and facilitates occupational risk assessment for the employees.     

Raman spectra of polycrystalline microdiamond inclusions in zircons,and ultrahigh-pressure metamorphism of a quartzofeldspathic rock from the Erzgebirge terrane,Germany

ABSTRACT

Polycrystalline microdiamonds are rare in ultrahigh-pressure (UHP) rocks worldwide. Among samples collected at Erzgebirge, Germany, we found abundant polycrystalline microdiamonds as inclusions in zircons from a quartzofeldspathic rock. To illuminate their origin and forming age, we investigated morphologies and Raman spectra of 52 microdiamond inclusions, and dated the zircon host. The zircons have low Th/U values (0.03–0.07) and a concordia U/Pb age of 335.8 ± 1.9 Ma. Polycrystalline diamond (10–40 µm) consists of many fine-grained crystals (1.5–3 µm) with different orientations; discrete single diamonds (2–20 µm) are rare. All measured Raman spectra show an intense diamond band at 1332–1328 cm^?1 and have a negative correlation with full width at half maximum (FWHM) of 5.8–11.3 cm^?1. These data combined with previously reported diamond band data (1331–1337 cm^?1) are compatible with those of diamond inclusions in various host minerals from other UHP terranes, but are different from those of ureilite diamonds. The Erzgebirge microdiamonds in zircon do not display visible disordered sp³-carbon, but show downshifting of the Raman band from the ideal value (1332 cm^?1), and have a broader diamond band (FWHM >3 cm^?1) than those of well-ordered diamonds. These features may reflect imperfect ordering due to rapid nucleation/crystallization during UHP metamorphism and rapid exhumation of the UHP terrane. Graphite inclusions in zircon show a typical G-band at 1587 cm^?1. Our study together with previously reported C-isotopic compositions (δ¹³C, ?17 to ?27‰) of diamond and occurrences of fluid/melt inclusions in diamond and garnet indicates that Erzgebirge microdiamonds are metamorphic, have an organic carbon source, and crystallized from aqueous fluids. Limited long-range ordering suggested by the Raman spectra is a function of the P–T time of crystallization and subsequent thermal annealing on decompression. Combined with regional geology, our work further constrains the tectonic evolution of the Erzgebirge terrane.