Arsenic distribution and pathway scenarios for sediments and water in a peri-urban Mongolian small-scale coal mining area (Nalaikh District,Ulaanbaatar)

The distribution of arsenic (As) in environmental compartments is investigated in the Nalaikh Depression of N-Mongolia. In Nalaikh, lignite coal is mined by artisanal small-scale mining (ASM) approaches. Because As is often associated with sulfuric minerals in coal, it was hypothesized that enrichment of As is related to coal ASM. A second hypothesis considered coal combustion in power plants, and stoves are a key source of As in the local environment. Three mobilization and distribution scenarios were developed for potential As pathways in this semiarid environment. About 43 soil and 14 water sites were analyzed for As concentrations and meaningful parameters in soil and water. About 28 topsoil samples were analyzed in surface-subsurface pairs in order to identify potential eolian surface enrichment. Additionally, fluvial-alluvial sediments and geogenic and anthropogenic deposits were sampled. Water was sampled as surface water, groundwater, precipitation, and industrial water. Results show that As does not pose a ubiquitous risk in the Nalaikh Depression. However, locally and specifically in water, As concentrations may exceed the WHO guideline value for drinking water by up to a factor of 10. A carefully selected sampling strategy allows the evaluation of the distribution scenarios, which reveals a combination of (a) geogenic As in groundwater and distribution via surface water with (b) anthropogenic As redistribution via eolian pathways. An immediate linkage between As redistribution and coal mining is not evident. However, As distribution in fly ash from coal combustion in the local power plant and yurt settlements is the most likely As pathway. Hence, the results indicate the potential influence of diffuse, low-altitude sources on As emission to the environment. As such, this study provides a good example for As distribution under semiarid climate conditions influenced by geogenic and anthropogenic factors.

     

Occurrence and temporal variations of TMDD in the river Rhine,Germany

Background, aim, and scope

The chemical substance 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) is a non-ionic surfactant used as an industrial defoaming agent and in various other applications. Its commercial name is Surynol 104® and the related ethoxylates are also available as Surfynol® 420, 440, 465 and 485 which are characterized by different grades of ethoxylation of TMDD at both hydroxyl functional groups. TMDD and its ethoxylates offer several advantages in waterborne industrial applications in coatings, inks, adhesives as well as in paper industries. TMDD and its ethoxylates can be expected to reach the aquatic environment due its widespread use and its physico-chemical properties. TMDD has previously been detected in several rivers of Germany with concentrations up to 2.5?µg/L. In the United States, TMDD was also detected in drinking water. However, detailed studies about its presence and distribution in the aquatic environment have not been carried out so far. The aim of the present study was the analysis of the spatial and temporal concentration variations of TMDD in the river Rhine at the Rheingütestation Worms (443.3 km). Moreover, the transported load in the Rhine was investigated during two entire days and 7 weeks between November 2007 and January 2008.

Materials and methods

The sampling was carried out at three different sampling points across the river. Sampling point MWL1 is located in the left part of the river, MWL2 in the middle part, and MWL4 in the right part. One more sampling site (MWL3) was run by the monitoring station until the end of 2006, but was put out of service due to financial constrains. The water at the left side of the river Rhine (MWL1) is influenced by sewage from a big chemical plant in Ludwigshafen and by the sewage water from this city. The water at the right side of the river Rhine (MWL4) is largely composed of the water inflow from river Neckar, discharging into Rhine 14.9 km upstream from the sampling point and of communal and industrial wastewater from the city Mannheim. The water from the middle of the river (MWL2) is largely composed of water from the upper Rhine. Water samples were collected in 1-L bottles by an automatic sampler. The water samples were concentrated by use of solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). The quantification was carried out with the internal standard method. Based on these results, concentration variations were determined for the day profiles and week profiles. The total number of analyzed samples was 219.

Results

The results of this study provide information on the temporal concentration variability of TMDD in river Rhine in a cross section at one particular sampling point (443.3 km). TMDD was detected in all analyzed water samples at high concentrations. The mean concentrations during the 2 days were 314 ng/L in MWL1, 246 ng/L in MWL2, and 286 ng/L in MWL4. The variation of concentrations was low in the day profiles. In the week profiles, a trend of increasing TMDD concentrations was detected particularly in January 2008, when TMDD concentrations reached values up to 1,330 ng/L in MWL1. The mean TMDD concentrations during the week profiles were 540 ng/L in MWL1, 484 ng/L in MWL2, and 576 ng/L in MWL4. The loads of TMDD were also determined and revealed to be comparable in all three sections of the river. The chemical plant located at the left side of the Rhine is not contributing additional TMDD to the river. The load of TMDD has been determined to be 62.8 kg/d on average during the entire period. By extrapolation of data obtained from seven week profiles the annual load was calculated to 23 t/a.

Discussion

The permanent high TMDD concentrations during the investigation period indicate an almost constant discharge of TMDD into the river. This observation argues for effluents of municipal wastewater treatment plants as the most likely source of TMDD in the river. Another possible source might be the degradation of ethoxylates of TMDD (Surfynol® series 400), in the WWTPs under formation of TMDD followed by discharge into the river. TMDD has to be considered as a high-production-volume (HPV) chemical based on the high concentrations found in this study. In the United States, TMDD is already in the list of HPV chemicals from the Environmental Protection Agency (EPA). However, the amount of TMDD production in Europe is unknown so far and also the biodegradation rates of TMDD in WWTPs have not been investigated.

Conclusions

TMDD was found in high concentrations during the entire sampling period in the Rhine river at the three sampling points. During the sampling period, TMDD concentrations remained constant in each part of the river. These results show that TMDD is uniformly distributed in the water collected at three sampling points located across the river. ‘Waves’ of exceptionally high concentrations of TMDD could not be detected during the sampling period. These results indicate that the effluents of WWTPs have to be considered as the most important sources of TMDD in river Rhine.

Recommendations and perspectives

Based also on the occurrence of TMDD in different surface waters of Germany with concentrations up to 2,500 ng/L and its presence in drinking water in the USA, more detailed investigations regarding its sources and distribution in the aquatic environment are required. Moreover, the knowledge with respect to its ecotoxicity and its biodegradation pathway is scarce and has to be gained in more detail. Further research is necessary to investigate the rate of elimination of TMDD in municipal and industrial wastewater treatment plants in order to clarify the degradation rate of TMDD and to determine to which extent effluents of WWTPs contribute to the input of TMDD into surface waters. Supplementary studies are needed to clarify whether the ethoxylates of TMDD (known as Surfynol 400® series) are hydrolyzed in the aquatic environment resulting in formation of TMDD similar to the well known cleavage of nonylphenol ethoxylates into nonylphenols. The stability of TMDD under anaerobic conditions in groundwater is also unknown and should be studied.

     

Characterization of On-Road Vehicle NO Emissions by a TILDAS Remote Sensor

ABSTRACT

A tunable infrared laser differential absorption spectrometer (TILDAS) was used to remotely sense the nitric oxide (NO) emissions from 1,473 on-road vehicles. The real-world measurement precision of this instrument in the limit of low NO concentration is 5 ppm of the vehicle exhaust, which corresponds to a 3o detection limit of 15 ppm. Our analysis of the distribution of negative concentration measurements produced during this experiment supports this claim, showing that the instrumental noise for this set of measurements was at most 8 ppm in the limit of low NO concentration. The high sensitivity of this instrument allowed us to measure the NO emissions of even the cleanest vehicles. The measured vehicle fleet NO emissions closely fit a gamma distribution with 10% of the fleet contributing about 50% of the total fleet emissions. Newer vehicles had lower NO emissions than older ones, but high NO emitters were found in every vehicle age cohort. On a vehicle-by-vehicle basis, NO emissions correlated very weakly with vehicle velocity, acceleration, power per unit mass, carbon monoxide (CO) emissions, and hydrocarbon (HC) emissions. High NO emitting vehicles could not be identified by remote sensing of CO or HC emissions and vice versa. When we compared the NO emissions for 117 vehicles measured more than one time, about half of the high NO emitters were found to be very consistent, while the other half varied significantly.     

A COMPARISON OF HAND- AND SPLINE-DRAWN PRECIPITATION MAPS FOR MOUNTAINOUS MONTANA1

ABSTRACT: Average annual precipitation for the period 1961–1990 was estimated for a mountainous region in Montana with a Laplacian thin-plate spline (ANUSPLIN) and compared to a hand-drawn map. Input data included latitude, longitude, and elevation from a three-arc-second U.S. Geological Survey Digital Elevation Model of the Bozeman and Billings 1 × 2 topographic quadrangles and precipitation data at 96 stations. The two maps are similar in appearance. Digital comparison of the two maps with ARC/INFO's Grid tools shows that mean annual precipitation for the hand-contoured map is 22.9 inches and for the ANUSPLIN map is 23.7 inches. Of the 5,760,000 cells, 53 percent showed no difference between ANUSPLIN and hand-drawn maps; 19 percent showed a two-inch difference, and 28 percent showed more than 2 inches difference. Input data and model output at the same location are not different (standard deviation 1.77, p-value 0.76). Hand-drawn maps show two inches more precipitation during the 1961–90 period than during the 1941–1970 period. Similarly, measured data at 73 sites for the period 1961–1990 are on average 2.4 inches higher than the same stations during the 1941–1970 period. The difference is significant (p-value > 0.0001).     

OFF-LINE STORMWATER DETENTION SYSTEMS1

ABSTRACT: This paper looks at the use of off-line detention systems as a means of stormwater management. Conventional detention basins are typically designed and built as in-line systems in which all runoff is directed to the basin. Off-line systems are designed so that only a portion of the runoff is directed to the basin. Several simulation experiments were run to examine the behavior of in-line and off-line systems designed to reduce the peak flow from a developed area to the pre-development level. The results demonstrate that off-line systems require considerably less storage than in-line systems to achieve the same management goal. The results also show that off-line and in-line systems have significantly different flow-duration characteristics with the off-line system generally producing lower flows over longer periods. Unfortunately, off-line systems may exacerbate downstream flooding problems, especially when used in the upper portions of a watershed. Nevertheless, an off-line system can be an alternative to in-line detention in many cases.     

A European model for waste and material flows

The use of materials and the generation of waste are linked to economic activities and in many projections these are assumed to be a constant ratio of the economic activities. This may be the case considering detailed economic activities and unchanged technology. However, the assumption of constant coefficients is questionable when linking material use and waste generation to aggregated economic activities. Therefore, in this paper, econometrics is used to test the assumption of constant waste coefficients empirically. The analyses show that an assumption of constant waste coefficients is not supported, generally, and a model allowing for trendwise changing coefficients is developed and used for projections of waste and material flows in 25 European countries.     

Links among nitrification, nitrifier communities, and edaphic properties in contrasting soils receiving dairy slurry

Soil biotic and abiotic factors strongly influence nitrogen (N) availability and increases in nitrification rates associated with the application of manure. In this study, we examine the effects of edaphic properties and a dairy (Bos taurus) slurry amendment on N availability, nitrification rates and nitrifier communities. Soils of variable texture and clay mineralogy were collected from six USDA-ARS research sites and incubated for 28 d with and without dairy slurry applied at a rate of ~300 kg N ha(-1). Periodically, subsamples were removed for analyses of 2 M KCl extractable N and nitrification potential, as well as gene copy numbers of ammonia-oxidizing bacteria (AOB) and archaea (AOA). Spearman coefficients for nitrification potentials and AOB copy number were positively correlated with total soil C, total soil N, cation exchange capacity, and clay mineralogy in treatments with and without slurry application. Our data show that the quantity and type of clay minerals present in a soil affect nitrifier populations, nitrification rates, and the release of inorganic N. Nitrogen mineralization, nitrification potentials, and edaphic properties were positively correlated with AOB gene copy numbers. On average, AOA gene copy numbers were an order of magnitude lower than those of AOB across the six soils and did not increase with slurry application. Our research suggests that the two nitrifier communities overlap but have different optimum environmental conditions for growth and activity that are partly determined by the interaction of manure-derived ammonium with soil properties.     

Higher Cd adsorption on biogenic elemental selenium nanoparticles

Cadmium (Cd) is a carcinogenic metal contaminating the environment and ending up in wastewaters. There is therefore a need for improved methods to remove Cd by adsorption. Biogenic elemental selenium nanoparticles have been shown to adsorb Zn, Cu and Hg, but these nanoparticles have not been tested for Cd removal. Here we studied the time-dependency and adsorption isotherm of Cd onto biogenic elemental selenium nanoparticles using batch adsorption experiments. We measured ζ-potential values to assess the stability of nanoparticles loaded with Cd. Results show that the maximum Cd adsorption capacity amounts to 176.8 mg of Cd adsorbed per g of biogenic elemental selenium nanoparticles. The ζ-potential of Cd-loaded nanoparticles became less negative from ?32.7 to ?11.7 mV when exposing nanoparticles to an initial Cd concentration of 92.7 mg L^?1. This is the first study that demonstrates the high Cd uptake capacity of biogenic elemental selenium nanoparticles, of 176.8 mg g^?1, when compared to that of traditional adsorbents such as carboxyl-functionalized activated carbon, of 13.5 mg g^?1. An additional benefit is the easy solid–liquid separation by gravity settling due to coagulation of Cd-loaded biogenic elemental selenium nanoparticles.