Mercury (Hg) emissions from domestic biomass combustion for space heating

Three mercury (Hg) species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and fine particulate-bound mercury (PBM_2.5)) were measured in the stack of a small scale wood combustion chamber at 400 °C, in the stack of an advanced wood boiler, and in two areas influenced by wood combustion. The low temperature process (lab-scale) emitted mostly GEM (∼99% when burning wood pellets and ∼95% when burning unprocessed wood). The high temperature wood boiler emitted a greater proportion of oxidized Hg (approximately 65%) than the low temperature system. In field measurements, mean PBM_2.5 concentrations at the rural and urban sites in winter were statistically significantly higher than in warmer seasons and were well correlated with Delta-C concentrations, a wood combustion indictor measured by an aethalometer (UV-absorbable carbon minus black carbon). Overall the results suggest that wood combustion may be an important source of oxidized mercury (mostly in the particulate phase) in northern climates in winter.     

Germanium in the soil-plant system—a review

Germanium (Ge) is widespread in the Earth’s crust. As a cognate element to silicon (Si), Ge shows very similar chemical characteristics. Recent use of Ge/Si to trace Si cycles and changes in weathering over time, growing demand for Ge as raw material, and consequently an increasing interest in Ge phytomining have contributed to a growing interest in this previously rather scarcely considered element in geochemical studies. This review deals with the distribution of Ge in primary minerals and surface soils as well as the factors influencing the mobility of Ge in soils including the sequestration of Ge in secondary mineral phases and soil organic matter. Furthermore, the uptake and accumulation of Ge in plants and effects of plant-soil relationships on the availability of Ge in soils and the biogeochemical cycling of Ge are discussed. The formation of secondary soil minerals and soil organic matter are of particular importance for the concentration of Ge in plant-available forms. The transfer from soil to plant is usually low and shows clear differences between species belonging to the functional groups of grasses and forbs. Possible uptake mechanisms in the rhizosphere are discussed. However, the processes that are involved in the formation of plant-available Ge pools in soils and consequently its biogeochemical cycling are not yet well understood. There is, therefore, a need for future studies on the uptake mechanisms and stoichiometry of Ge uptake under field conditions and plant-soil-microbe interactions in the rhizosphere as well as the chemical speciation in different plant parts.     

Estimating the spatial scale of herbicide and soil interactions by nested sampling, hierarchical analysis of variance and residual maximum likelihood

An unbalanced nested sampling design was used to investigate the spatial scale of soil and herbicide interactions at the field scale. A hierarchical analysis of variance based on residual maximum likelihood (REML) was used to analyse the data and provide a first estimate of the variogram. Soil samples were taken at 108 locations at a range of separating distances in a 9 ha field to explore small and medium scale spatial variation. Soil organic matter content, pH, particle size distribution, microbial biomass and the degradation and sorption of the herbicide, isoproturon, were determined for each soil sample. A large proportion of the spatial variation in isoproturon degradation and sorption occurred at sampling intervals less than 60 m, however, the sampling design did not resolve the variation present at scales greater than this. A sampling interval of 20-25 m should ensure that the main spatial structures are identified for isoproturon degradation rate and sorption without too great a loss of information in this field.     

Hot filter/impinger and dilution sampling for fine particulate matter characterization from ferrous metal casting processes

A study using two stack-sampling methodologies for collecting particulate matter (PM) emissions was conducted using a hot filter followed by a cold impinger sampling train and a dilution sampler. Samples were collected from ferrous iron metal casting processes that included pouring molten iron into a sand mold containing an organic binder, metal cooling, removal of the sand from the cooled casting (shakeout), and postshakeout cooling. The shakeout process contributed more to PM emissions than the metal pouring and cooling processes. Particulate matter less than 2.5 microm in aerodynamic diameter (PM2.5) mass emissions for the entire casting cycle ranged from 3.4 to 4.7 lb/t of metal for the hot filter/impinger method and from 0.8 to 1.8 lb/t of metal for the dilution method. Most of the difference was due to PM captured by the impingers, much of which was probably dissolved gases rather than condensable vapors. Of the PM fraction captured by the impingers, 96-98% was organic in nature. The impinger PM fraction contributed 32-38% to the total suspended particle mass and caused a factor of 2-4 positive bias for PM2.5 emissions. For the pouring and cooling processes only, the factor increased to over seven times.     

Environmental monitoring study of selected veterinary antibiotics in animal manure and soils in Austria

LC-MS/MS was used for determination of selected tetracyclines, sulfonamides, trimethoprim, and fluoroquinolones in manure samples of pig, chicken and turkey, as well as arable soils fertilized with manure. Recoveries from spiked samples ranged from 61 to 105%. Method quantification limits were set to 100 microg/kg for all substances. Analysis of 30 pig manure, 20 chicken and turkey dung, and 30 lyophilized soil samples taken in Austria revealed that in pig manure up to 46 mg/kg chlortetracycline, 29 mg/kg oxytetracycline and 23 mg/kg tetracycline could be detected. As representatives of the group of sulfonamides, sulfadimidine in pig manure and sulfadiazine in chicken and turkey dung were detected in significant amounts (maximum concentration, 20 and 91 mg/kg, respectively). Enrofloxacin was particularly observed in chicken and turkey samples. Positive detection of chlortetracycline, enrofloxacin, and ciprofloxacin, in soil samples should be outlined as most important results of this study.     

HPLC determination of chlorate metabolism in bovine ruminal fluid

Salmonella and Escherichia coli are two bacteria that are important causes of human and animal disease worldwide. Chlorate is converted in the cell to chlorite, which is lethal to these bacteria. An HPLC procedure was developed for the rapid analysis of chlorate (ClO(3)(-)), nitrate (NO(3)(-)), and nitrite (NO(2)(-)) ions in bovine ruminal fluid samples. Standard curves for chlorite, nitrite, nitrate, and chlorate were well defined linear curves with R(2) values of 0.99846, 0.99106, 0.99854, and 0.99138, respectively. Concentrations of chlorite could not be accurately determined in bovine ruminal fluid because chlorite reacts with or binds a component(s) or is reduced to chloride in bovine ruminal fluid resulting in low chlorite measurements. A standard curve ranging from 25 to 150 ppm ClO(3)(-) ion was used to measure chlorate fortified into ruminal fluid. The concentration of chlorate was more rapidly lowered (P < 0.01) under anaerobic compared to aerobic incubation conditions. Chlorate alone or chlorate supplemented with the reductants sodium lactate or glycerol were bactericidal in anaerobic incubations. In anaerobic culture, the addition of sodium formate to chlorate-fortified ruminal fluid appeared to decrease chlorate concentrations; however, formate also appeared to moderate the bactericidal effect of chlorate against E. coli. Addition of the reductants, glycerol or lactate, to chlorate-fortified ruminal fluid did not increase the killing of E. coli at 24 h, but may be useful when the reducing equivalents are limiting as in waste holding reservoirs or composting systems required for intense animal production.     

The IMPROVE_A temperature protocol for thermal/optical carbon analysis: maintaining consistency with a long-term database

Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 degrees C for OC1, 280 degrees C for OC2, 480 degrees C for OC3, and 580 degrees C for OC4 in a helium (He) carrier gas and 580 degrees C for EC1, 740 degrees C for EC2, and 840 degrees C for EC3 in a 98% He/2% oxygen (O2) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O2 in the pure He carrier gas shows that O2 levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.     

Human–wildlife coexistence in a changing world

Human–wildlife conflict (HWC) is a key topic in conservation and agricultural research. Decision makers need evidence-based information to design sustainable management plans and policy instruments. However, providing objective decision support can be challenging because realities and perceptions of human–wildlife interactions vary widely between and within rural, urban, and peri-urban areas. Land users who incur costs through wildlife argue that wildlife-related losses should be compensated and that prevention should be subsidized. Supporters of human–wildlife coexistence policies, such as urban-dwelling people, may not face threats to their livelihoods from wildlife. Such spatial heterogeneity in the cost and benefits of living with wildlife is germane in most contemporary societies. This Special Section features contributions on wildlife-induced damages that range from human perspectives (land use, psychology, governance, local attitudes and perceptions, costs and benefits, and HWC and coexistence theory) to ecological perspectives (animal behavior). Building on current literature and articles in this section, we developed a conceptual model to help frame HWC and coexistence dimensions. The framework can be used to determine damage prevention implementation levels and approaches to HWC resolution. Our synthesis revealed that inter- and transdisciplinary approaches and multilevel governance approaches can help stakeholders and institutions implement sustainable management strategies that promote human–wildlife coexistence.     

Detection and attribution of lake-level dynamics in north-eastern central Europe in recent decades

The lake-rich glacial landscapes of north-eastern central Europe play an important role in the preservation and use of water resources, including protection of biodiversity, carbon storage and promotion of tourism. With a view to the last c. 20 years and the future, a regional ‘syndrome of water shortage’ has been frequently stated, which impairs particularly peatlands, flowing waters and lakes. Accordingly, the overall question addressed in this study is: What can regional and local gauging records tell us about decadal hydrological changes of lakes and their catchments? In the study area, most of the gauging records of lakes begin only in the late 1990s. Forty-five lake-level records were analysed by hierarchical agglomerative clustering, looking for the trend in the 1999–2008 time window. The analyses show that lake levels had varying dynamics, namely a negative, unclear or even a positive trend. The proportional shares of these three groups are 23 (51 %) to 15 (34 %) to 7 lakes (15 %), respectively. In group 1, largely groundwater-fed lakes, lake-level changes depend on groundwater-level changes. These are controlled by decreasing groundwater recharge in the catchments, which are caused by specific seasonal weather conditions in the observation period, and the impact of the dominating pine forests, which consume high quantities of water. In group 2, mainly stream lakes, direct human impact drives the lake levels through the management of weirs and ground sills. Nearly all lakes in group 3, consisting of river, stream and spring lakes, were subject to impoundment measures initiated by local rewetting projects. Thus, an important finding with respect to the impact of climate and land use is the fact that the (‘natural’) lakes of the region, primarily fed by groundwater and precipitation, show a predominantly negative lake-level trend in the period studied. Beyond the 10-year-time window analysed, further regional data show that periodic lake-level fluctuations with amplitudes of c. 1–2(–3) m are characteristic for regional groundwater-fed lakes.