Overview and assessment of techniques to measure ammonia emissions from animal houses: the case of the Netherlands

In order to comply with the ammonia (NH(3)) emission reduction assigned to the Netherlands development of new measures are needed, which should be supported by fast and accurate measurements to arrive at new estimates of the NH(3) emission from each agricultural source. This paper gives an overview of the current methods used in the Netherlands to measure NH(3) emissions from animal houses, and provides alternative methods for some particular situations. For mechanically ventilated animal houses, passive flux samplers placed in the ventilation shafts of the animal house are presented as alternative to measure a larger number of animal houses (replicates) with the same housing system at a low price. For naturally ventilated animal houses, when mixing in the animal house is not good enough to allow measurements within the animal house (internal tracer gas ratio method), two measurement methods are discussed: the Gaussian plume dispersion model, which is usually not suitable for agricultural situations, and the flux frame method, which is not always applicable because of distortion of the flow around the building. Finally, for animal houses with outside yards for the animals, there are at this moment no methods available to measure the NH(3) emissions from these complex situations, although quick box methods (for the outside yards) and a combination of a backward Lagrangian stochastic model with open-path concentration measurements with a tunable diode laser (TDL), look promising.     

Bioavailability of contaminants estimated from uptake rates into soil invertebrates

It is often argued that the concentration of a pollutant inside an organism is a good indicator of its bioavailability, however, we show that the rate of uptake, not the concentration itself, is the superior predictor. In a study on zinc accumulation and toxicity to isopods (Porcellio scaber) the dietary EC(50) for the effect on body growth was rather constant and reproducible, while the internal EC(50) varied depending on the accumulation history of the animals. From the data a critical value for zinc accumulation in P. scaber was estimated as 53 microg/g/wk. We review toxicokinetic models applicable to time-series measurements of concentrations in invertebrates. The initial slope of the uptake curve is proposed as an indicator of bioavailability. To apply the dynamic concept of bioavailability in risk assessment, a set of representative organisms should be chosen and standardized protocols developed for exposure assays by which suspect soils can be evaluated.     

Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Dissolved oxygen and dietary phosphorus modulate utilization and effluent partitioning of phosphorus in rainbow trout (Oncorhynchus mykiss) aquaculture

Phosphorus (P) is the limiting nutrient in freshwater primary production, and excessive levels cause premature eutrophication. P levels in aquaculture effluents are now tightly regulated. Increasing our understanding of waste P partitioning into soluble, particulate, and settleable fractions is important in the management of effluent P. When water supply is limited, dissolved oxygen concentration (DO) decreases below the optimum levels. Therefore, we studied effects of DO (6 and 10mg/L) and dietary P (0.7 and 1.0% P) on rainbow trout growth, P utilization, and effluent P partitioning. Biomass increased by 40% after 3 weeks. DO at 10mg/L significantly increased fish growth and feed efficiency, and increased the amount of P in the soluble fraction of the effluent. Soluble effluent P was greater in fish fed 1.0% P. DO increases fish growth and modulates P partitioning in aquaculture effluent.     

The impact of pumped water from a de-watered Magnesian limestone quarry on an adjacent wetland: Thrislington, County Durham, UK

Although quarrying is often cited as a potential threat to wetland systems, there is a lack of relevant, quantitative case studies in the literature. The impact of pumped groundwater discharged from a quarry into a wetland area was assessed relative to reference conditions in an adjacent fen wetland that receives only natural runoff. Analysis of vegetation patterns at the quarry wetland site, using Detrended Correspondence Analysis and the species indicator values of Ellenberg, revealed a clear disparity between community transitions in the quarry wetland and the reference site. Limited establishment of moisture-sensitive taxa, the preferential proliferation of robust wetland species and an overall shift towards lower species diversity in the quarry wetland were explicable primarily by the physico-chemical environment created by quarry dewatering. This encompassed high pH (up to 12.8), sediment-rich effluent creating a nutrient-poor substrate with poor moisture retention in the quarry wetland, and large fluctuations in water levels.     

Partitioning of polychlorinated biphenyls in octanol/water, triolein/water, and membrane/water systems

The use of the octanol/water partition constant (Kow) as a surrogate parameter for lipid/water partitioning of persistent organic pollutants (POPs) was reassessed by comparing the measured Kow of 12 selected polychlorinated biphenyl congeners (PCBs) with partition constants in triolein/water (Ktw) and membrane/water (Kmw) systems. Kow and Ktw were measured by the slow-stirring method. Kmw was measured by an adaptation of the slow-stirring method using suspensions of phosphatidylcholine and phosphatidylserine liposomes. Partitioning of POPs to octanol, triolein, and liposomes is similar but not equal. The log-log correlation for Kow and Ktw is excellent (r2 = 0.982) and that for Kow and Kmw is somewhat weaker (r2 = 0.856). Ktw values are greater than Kow by a factor of 1.6. Kmw of some PCB congeners exceed both Kow and Ktw by an order of magnitude. The differences are attributed to different PCB activity coefficients in the different lipid phases. The results imply that Kow can be used as a reasonable conservative estimate of lipid/water partitioning. But the observed differences between Kow and Kmw also indicate that using Kow to predict accumulation of POPs, particularly highly hydrophobic ones, in the polar lipids of organisms will underestimate their concentrations at equilibrium.     

Degradation of 2,4,6-trinitrotoluene by selected helophytes

Four emergent plants (helophytes, synonyms emersion macrophytes, marsh plants, etc.) Phragmites australis, Juncus glaucus, Carex gracillis and Typha latifolia were successfully used for degradation of TNT (2,4,6-trinitrotoluene) under in vitro conditions. The plants took up and transformed more than 90% of TNT from the medium within ten days of cultivation. The most efficient species was Ph. australis which took up 98% of TNT within ten days. The first stable degradation products 4-amino-2,6-dinitrotoluene (4-ADNT) and 2-amino-4,6-dinitrotoluene (2-ADNT) were identified and analysed during the cultivation period. [14C] TNT was used for the detection of TNT degradation products and their compartmentalization in plant tissues after two weeks of cultivation. Forty one percent of 14C was detected as insoluble or bound in cell structures: 34% in roots and 8% in the aerial parts. These results open the perspective of using the above-mentioned plants for the remediation of TNT contaminated waters.     

Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites

The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Tylosin sorption to silty clay loam soils, swine manure, and sand

The objectives of this study were to assess sorption and desorption of tylosin, a macrolide antimicrobial chemical used in swine, cattle, and poultry production, in three silty clay loam soils of South Dakota and compare soil sorption to sand and manure sorption. The silty clay loam soils, from a toposequence in eastern South Dakota, standardized sand samples, and swine manure were used in 24-h batch sorption studies with tylosin concentrations ranging from 25 to 232 micro mole/L. Desorption from soil was conducted over a four-day period. Partition coefficients, based on the Freundlich isotherm (K(f)) or K(d) values, were calculated. K(f) values for the silty clay loams were similar, not influenced by landscape position, and averaged 1,350 with isotherm slopes ranging from 0.85 to 0.93. K(f) values for sand were dependent on solution/sand ratios and pH, ranging from 1.4 to 25.1. K(d) values of manure were dependent on the solution type and ranged from 840 L/kg with urine to about 175 L/kg when sorbed from water. Desorption of tylosin from each soil over the four-day period was < 0.2% of the amount added. The soils' high K(f) values and low desorption amounts suggest that once tylosin is in these soils, leaching to lower depths may not occur. However, this does not preclude runoff with soil eroded particles. If tylosin reaches a sand aquifer, through bypass flow or other mechanism(s), movement in the aquifer most likely would occur.