Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part II. Application to sediment and sludge samples in Austria

Soxhlet extraction and high-performance liquid chromatography (HPLC) coupled to tandem mass spectrometry detection (MS/MS) was used for the determination of selected quaternary ammonium compounds (QACs) in solid samples. The method was applied for the determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds in sediment and sludge samples in Austria. The overall method quantification limits range from 0.6 to 3 microg/kg for sediments and from 2 to 5 microg/kg for sewage sludges. Mean recoveries between 67% and 95% are achieved. In general sediments were especially contaminated by C12 chain benzalkonium chloride (BAC-C12) as well as by the long C-chain dialkyldimethylammonium chloride (DDAC-C18) with a maximum concentration of 3.6 mg/kg and 2.1mg/kg, respectively. Maxima of 27 mg/kg for DDAC-C10, 25 mg/kg for BAC-C12 and 23 mg/kg for BAC-C14 were determined for sludge samples. The sums of the 12 selected target compounds range from 22 mg/kg to 103 mg/kg in the sludge samples.     

Water quantity and quality dynamics of the THC — Tuyamuyun Hydroengineering Complex — And implications for reservoir operation

Background In the Aral Sea basin, safe water resources are scarce and steadily becoming scarcer. Particularly high quality water is going to become a rare good. The object of the study was the Tuyamuyun Hydroengineering Complex (THC), a complex of artificial water reservoirs located in the lower Amu Darya River, which provides water for irrigation, industry, and drinking for the lower Amu Darya region. The focus was on operation of one of its four reservoirs, the Kaparas, which is mainly used for drinking water supply. The objective includes the investigation of impacts of conventional operation schemes on the reservoir water quality for improving drinking water quality (salinity). Basic operation rules for Kaparas, which can be considered as representative for conventional dam operation under dry year conditions, had to be identified and improved operation schemes derived. Methods Existing data archives were analysed, and further data were acquired from field surveys, data processing and modelling studies. Historical data were identified, which are appropriate to determine representative schemes for the conventional operation. For the simulation of time-dependent and depth-dependent changes of reservoir salinisation, the reservoir water quality model Lac was used and linked with the THC model. Results and Discussion Modelling results for the simulation of temperature dynamics and density stratification showed a sufficient congruence with the measured temperature profiles. The conformity of measured and calculated salt concentration is basically ensured. The reservoir, which fill with higher saline water at the end of the summer, aggravates the entrainment of high saline water in the entire water column. Conclusions The current conventional operation regime mainly leads to filling the Kaparas reservoir with high saline water during the winter months. Even in the event of starting with comparable low salinity levels, the simulation demonstrates the rapid deterioration of the reservoir water quality. Under dry year conditions, the WHO standards for drinking water will be exceeded by 30% after two years, so that the impact of dry years in the context of water stress becomes visible. Recommendations and Outlook Processed data and results are now available to identify enhanced reservoir operation strategies for salinity reduction by changing the period of reservoir filling and release, as well as to initiate a detailed analysis of how water deficits in dry years may be reduced by improved operation regimes. Using adapted and enhanced operation rules for THC reservoirs, the local population within the lower Aral Sea basin might be supplied with more potable water of higher quality in future.     

Aliphatic and polycyclic aromatic hydrocarbons in sediments of the Slovenian coastal area (Gulf of Trieste, northern Adriatic)

The distribution and sources of aliphatic and polycyclic aromatic hydrocarbons (PAH) were determined in sediments at seven sites around the Slovenian coastal area. The potential toxicological significance was also assessed using biological thresholds. The results of the analyses showed higher concentrations of hydrocarbons in the Port of Koper and in the Marina of Portoroz. The influence of pollution was also evident in rather higher concentrations of hydrocarbons in the surrounding area in the Bays of Koper and Piran. Concentrations of hydrocarbons decrease toward the central part of the Gulf of Trieste. The major component of the aliphatic fraction was the unresolved complex mixture. Concentrations of the total resolved aliphatic hydrocarbons were in a range from 689 to 3,164?ng?g^?1. Concentrations of the total PAHs were between 330 and 1,173?ng?g^?1. Polycyclic aromatic hydrocarbons are primarily of pyrolytic origin with some smaller contributions of the petrogenic, while the aliphatic are mostly of petrogenic origin with significant amounts of biogenic derived compounds of terrestrial and marine origin. Strong evidence of the diagenetic origin of perylene in the investigated area was also found. Quite a good linear relationship between PAH concentration and TOC and between aliphatic hydrocarbon concentrations and TOC was observed. The principal component analysis showed differences between the nearshore and offshore sites. In general, the investigated area is moderately contaminated by hydrocarbons. Concentrations of PAHs, hydrocarbons of high concern, are below the levels (effects range low and the effects range median) associated with adverse biological effects.     

Evaluation of solid particle number and black carbon for very low particulate matter emissions standards in light-duty vehicles

To reliably measure at the low particulate matter (PM) levels needed to meet California’s Low Emission Vehicle (LEV III) 3- and 1-mg/mile particulate matter (PM) standards, various approaches other than gravimetric measurement have been suggested for testing purposes. In this work, a feasibility study of solid particle number (SPN, d50 = 23 nm) and black carbon (BC) as alternatives to gravimetric PM mass was conducted, based on the relationship of these two metrics to gravimetric PM mass, as well as the variability of each of these metrics. More than 150 Federal Test Procedure (FTP-75) or Supplemental Federal Test Procedure (US06) tests were conducted on 46 light-duty vehicles, including port-fuel-injected and direct-injected gasoline vehicles, as well as several light-duty diesel vehicles equipped with diesel particle filters (LDD/DPF). For FTP tests, emission variability of gravimetric PM mass was found to be slightly less than that of either SPN or BC, whereas the opposite was observed for US06 tests. Emission variability of PM mass for LDD/DPF was higher than that of both SPN and BC, primarily because of higher PM mass measurement uncertainties (background and precision) near or below 0.1 mg/mile. While strong correlations were observed from both SPN and BC to PM mass, the slopes are dependent on engine technologies and driving cycles, and the proportionality between the metrics can vary over the course of the test. Replacement of the LEV III PM mass emission standard with one other measurement metric may imperil the effectiveness of emission reduction, as a correlation-based relationship may evolve over future technologies for meeting stringent greenhouse standards.

Implications: Solid particle number and black carbon were suggested in place of PM mass for the California LEV III 1-mg/mile FTP standard. Their equivalence, proportionality, and emission variability in comparison to PM mass, based on a large light-duty vehicle fleet examined, are dependent on engine technologies and driving cycles. Such empirical derived correlations exhibit the limitation of using these metrics for enforcement and certification standards as vehicle combustion and after-treatment technologies advance.     

Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers

A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver–Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.     

Spatial analysis of volatile organic compounds in South Philadelphia using passive samplers

Select volatile organic compounds (VOCs) were measured in the vicinity of a petroleum refinery and related operations in South Philadelphia, Pennsylvania, USA, using passive air sampling and laboratory analysis methods. Two-week, time-integrated samplers were deployed at 17 sites, which were aggregated into five site groups of varying distances from the refinery. Benzene, toluene, ethylbenzene, and xylene isomers (BTEX) and styrene concentrations were higher near the refinery’s fenceline than for groups at the refinery’s south edge, mid-distance, and farther removed locations. The near fenceline group was significantly higher than the refinery’s north edge group for benzene and toluene but not for ethylbenzene or xylene isomers; styrene was lower at the near fenceline group versus the north edge group. For BTEX and styrene, the magnitude of estimated differences generally increased when proceeding through groups ever farther away from the petroleum refining. Perchloroethylene results were not suggestive of an influence from refining. These results suggest that emissions from the refinery complex contribute to higher concentrations of BTEX species and styrene in the vicinity of the plant, with this influence declining as distance from the petroleum refining increases.

Implications: Passive sampling methodology for VOCs as discussed here is employed in recently enacted U.S. Environmental Protection Agency Methods 325A/B for determination of benzene concentrations at refinery fenceline locations. Spatial gradients of VOC concentration near the refinery fenceline were discerned in an area containing traffic and other VOC-related sources. Though limited, these findings can be useful in application of the method at such facilities to ascertain source influence.     

Multiple-year black carbon measurements and source apportionment using delta-C in Rochester, New York

Black carbon (BC), an important component ofthe atmospheric aerosol, has climatic, environmental, and human health significance. In this study, BC was continuously measured using a two-wavelength aethalometer (370 nm and 880 nm) in Rochester; New York, from January 2007 to December 2010. The monitoring site is adjacent to two major urban highways (I-490 and I-590), where 14% to 21% of the total traffic was heavy-duty diesel vehicles. The annual average BC concentrations were 0.76 microg/m3, 0.67 microg/m3, 0.60 microg/m3, and 0.52 microg/m3 in 2007, 2008, 2009, and 2010, respectively. Positive matrix factorization (PMF) modeling was performed using PM2.5 elements, sulfate, nitrate, ammonia, elemental carbon (EC), and organic carbon (OC) data from the US. Environmental Protection Agency (EPA) speciation network and Delta-C (UVBC370nm-BC880nm) data. Delta-C has been previously shown to be a tracer of wood combustion factor It was used as an input variable in source apportionment models for the first time in this study and was found to play an important role in separating traffic (especially diesel) emissions from wood combustion emissions. The result showed the annual average PM2.5 concentrations apportioned to diesel emissions in 2007, 2008, 2009, and 2010 were 1.34 microg/m3, 1.25 microg/m3, 1.13 microg/m3, and 0.97 microg/m3, respectively. The BC conditional probability function (CPF) plots show a large contribution from the highway diesel traffic to elevated BC concentrations. The measurements and modeling results suggest an impact of the US Environmental Protection Agency (EPA) 2007 Heavy-Duty Highway Rule on the decrease ofBC and PM2.5 concentrations during the study period.     

A model for interprovincial air pollution control based on futures prices

Based on the current status of research on tradable emission rights futures, this paper introduces basic market-related assumptions for China’s interprovincial air pollution control problem. The authors construct an interprovincial air pollution control model based on futures prices: the model calculated the spot price of emission rights using a classic futures pricing formula, and determined the identities of buyers and sellers for various provinces according to a partitioning criterion, thereby revealing five trading markets. To ensure interprovincial cooperation, a rational allocation result for the benefits from this model was achieved using the Shapley value method to construct an optimal reduction program and to determine the optimal annual decisions for each province. Finally, the Beijing–Tianjin–Hebei region was used as a case study, as this region has recently experienced serious pollution. It was found that the model reduced the overall cost of reducing SO₂ pollution. Moreover, each province can lower its cost for air pollution reduction, resulting in a win–win solution. Adopting the model would therefore enhance regional cooperation and promote the control of China’s air pollution.

Implications: The authors construct an interprovincial air pollution control model based on futures prices. The Shapley value method is used to rationally allocate the cooperation benefit. Interprovincial pollution control reduces the overall reduction cost of SO₂. Each province can lower its cost for air pollution reduction by cooperation.