Persistence of chlorpropham (CIPC) in the concrete flooring of potato stores

The loss of the sprout suppressant, chlorpropham (CIPC), to the fabric of potato stores is currently of concern due to the risk of potential cross contamination of other crops subsequently housed in these stores. HPLC UV/VIS and GCMS methods were successfully employed to detect CIPC in the concrete flooring of research and commercial potato stores with histories of between 1 and 26 years of use. The concentrations in identical research stores, with different numbers of applications, were in the range 0.58–5.7 and 3.4–112 μg g−1, suggesting the magnitude of contamination was influenced by the number of applications. Commercial store A, with a history of 18 seasons of applications (estimate of total CIPC applied 2040 kg), had concentrations varying between 6 and 48 μg g−1 in the top three centimetres, with more than 92% within the top centimetre. In contrast, commercial store B, with a history of less than five seasons of applications (estimate of total CIPC applied 319 kg), had concentrations varying between 0.58 and 304 μg g−1 in the top four centimetres, with less than 47% within the top centimetre. The difference in depth distributions between A and B may be due to the structural integrity of the concrete, which was much poorer in B. CIPC was persistent in all stores irrespective of the total quantities of CIPC applied and date of the final application

Some are more equal than others : the role of ‘keystone’ species in the degradation of recalcitrant substrates

Peer reviewedPublisher PD

When can gravitational-wave observations distinguish between black holes and neutron stars?

Gravitational-wave observations of compact binaries have the potential to uncover the distribution of masses and angular momenta of black holes and neutron stars in the universe. The binary components' physical parameters can be inferred from their effect on the phasing of the gravitational-wave signal, but a partial degeneracy between the components' mass ratio and their angular momenta limits our ability to measure the individual component masses. At the typical signal amplitudes expected by the Advanced Laser Interferometer Gravitational-wave Observatory (signal-to-noise ratios between 10 and 20), we show that it will in many cases be difficult to distinguish whether the components are neutron stars or black holes. We identify when the masses of the binary components could be unambiguously measured outside the range of current observations: a system with a chirp mass $\mathcal{M} \le 0.871$ M$_\odot$ would unambiguously contain the smallest-mass neutron star observed, and a system with \mathcal{M} \ge 2.786 \Msun must contain a black hole. However, additional information would be needed to distinguish between a binary containing two 1.35 M$_\odot$ neutron stars and an exotic neutron-star--black-hole binary. We also identify those configurations that could be unambiguously identified as black-hole binaries, and show how the observation of an electromagnetic counterpart to a neutron-star--black-hole binary could be used to constrain the black-hole spin.Comment: 5 pages, 4 figures. Final version to be published in Ap.J.Let

Effect of alcohol addition on the movement of petroleum hydrocarbon fuels in soil

Groundwater contamination by fuel spills from aboveground and underground storage tanks has been of growing concern in recent years. This problem has been magnified by the addition of oxygenates, such as ethanol and methyl-tertiary-butyl ether (MTBE) to fuels to reduce vehicular emissions to the atmosphere. These additives, although beneficial in reducing atmospheric pollution, may, however, increase groundwater contamination due to the co-solvency of petroleum hydrocarbons and by the provision of a preferential substrate for microbial utilisation. With the introduction of ethanol to diesel fuel imminent and the move away from MTBE use in many states of the USA, the environmental implications associated with ethanol additive fuels must be thoroughly investigated. Diesel fuel movement was followed in a 1-m soil column and the effect of ethanol addition to diesel fuel on this movement determined. The addition of 51% ethanol to diesel fuel was found to enhance the downward migration of the diesel fuel components, thus increasing the risk of groundwater contamination. A novel method using soil packcd HPLC columns allowed the influence of ethanol on individual aromatic hydrocarbon movement to be studied. The levels of ethanol addition investigated were at the current additive level (approx. 25%) for ethanol additive fuels in Brazil and values above (50%) and below (10%) this level. An aqueous ethanol concentration above 10% was required for any movement to occur. At 25% aqueous ethanol, the majority of hydrocarbons were mobilised and the retention behaviour of the soil column lessened. At 50% aqueous ethanol, all the hydrocarbons were found to move unimpeded through the columns. The retention behaviour of the soil was found to change significantly when both organic matter content and silt/clay content was reduced. Unexpectedly, sandy soil with low organic matter and low silt/clay was found to have a retentive behaviour similar to sandy subsoil with moderate silt/clay, but little organic matter. It was concluded that sand grains might have a more important role in the adsorption of petroleum hydrocarbons than first realised. This method has shown that soil packed HPLC columns can be used to provide a quick estimate of petroleum hydrocarbon, and possibly other organic contaminant, movement in a variety of different soil types

Development of a sensitive and rapid method for the measurement of total microbial activity using fluorescein diacetate (FDA) in a range of soils

Fluorescein diacetate (FDA) hydrolysis is widely accepted as an accurate and simple method for measuring total microbial activity in a range of environmental samples, including soils. Colourless fluorescein diacetate is hydrolysed by both free and membrane bound enzymes, releasing a coloured end product fluorescein which can be measured by spectrophotometry. The current method for measuring FDA hydrolysis in soils is limited in its application. FDA activity was very low in sandy and clayey soils. The low activity observed for these soil types was made difficult to measure by the original authors choice of solvent for terminating the hydrolysis reaction. Acetone (50% v/v) was found to be most efficient at stopping the hydrolysis reaction. During this study acetone (50% v/v) was found to cause a decrease of approximately 37% in the absorbance of fluorescein produced by the soil samples measured. Although this colour loss is independent of initial fluorescein concentration, it makes the measurement of FDA hydrolytic activity extremely difficult in soils with low microbial activity i.e. sandy and/or clayey soils. Chloroform/methanol (2:1 v/v) was found to successfully stop the hydrolysis reaction for up to 50 min in a range of soil samples without causing the loss of colour observed with acetone. By changing the solvent used for terminating the hydrolysis reaction, low activity soils could be measured successfully. Other parameters of the hydrolysis reaction were optimised for the measurement of soil samples including effect of pH. optimum temperature of incubation, amount of soil, time of incubation, amount of substrate and preparation of suitable standards. A new, more sensitive method is proposed adapted from the original method, which provides a more accurate determination of FDA hydrolysis in a wide range of soils

Determination of Chlorpropham (CIPC) residues, in the concrete flooring of potato stores, using quantitative (HPLC UV/VIS) and qualitative (GCMS) methods

Isopropyl-N-(3-chlorophenyl) carbamate (CIPC, common name Chlorpropham) is commonly used for post-harvest sprout inhibition in stored potatoes. It is applied as a thermal fog which results in loss to the fabric of the store and the atmosphere. Recently, there have been concerns in the United Kingdom because of cross contamination of other crop commodities that were stored in buildings with a history of CIPC usage. This cross contamination may have occurred because of retained residues in the fabric of the stores. The retention of CIPC in concrete is poorly understood; therefore the requirement for a robust analytical method for the detection and quantification of CIPC in concrete is a critical first step in tackling this problem. A method using High-Performance Liquid Chromatography with ultraviolet detection (HPLC UV/VIS) was validated. CIPC recoveries at three concentration levels (0.4, 4.0 and 40.0 µg g-1) were in the range of 90.7-97.0 % with relative standard deviations between 2.14-3.01 %. The limits of detection and quantification were 0.03 and 0.1 µg g-1 , respectively. This study confirmed that CIPC was persistent in concrete to a depth of 4 cm, with > 90 % within the top 1 cm of the flooring

Continuous Flow Generation of Acylketene Intermediates via Nitrogen Extrusion

A flow chemistry process for the generation and use of acylketene precursors through extrusion of nitrogen gas is reported. Key to the development of a suitable continuous protocol is the balance of reaction concentration against pressure in the flow reactor. The resulting process enables access to intercepted acylketene scaffolds using volatile amine nucleophiles and has been demonstrated on the gram scale. Thermal gravimetric analysis was used to guide the temperature set point of the reactor coils for a variety of acyl ketene precursors. The simultaneous generation and reaction of two reactive intermediates (both derived from nitrogen extrusion) is demonstrated

The risk of chlorpropham cross-contamination of grain in potato stores

The contamination of food with pesticide residues is of significant concern to consumers and legislation has been implemented worldwide to ensure compliance with Maximum Residue Levels of chemicals in food. The occurrence of the potato sprout inhibitor, isopropyl N-(3-chlorophenyl) carbamate (chlorpropham or CIPC) residues on cereals, such as wheat, is of concern as this chemical is not authorised for use on cereals, and therefore the route of unintentional contamination warrants further investigation. This study reports on the risk of CIPC cross-contamination of grain that was stored in a commercial potato store and provides a method for low level quantification of CIPC in cereals. A High Performance Liquid Chromatography (HPLC UV/VIS) method for quantifying residues of CIPC in grains was successfully validated and the presence of CIPC was confirmed by Gas Chromatography Mass Spectrometry (GCMS). The magnitude of contamination in the grain was influenced by: (I) direct contact with the flooring of the store; (II) the headspace directly above the concrete surface and within the store itself and (III) contaminated dust/CIPC particles in the store atmosphere. Cross contamination is feasible irrespective of the CIPC concentrations in the concrete flooring and even with storage of grain at an elevated height above the concrete, suggesting that the route of cross contamination is a complex process involving physical and chemical (volatilization) factors. The results are significant for recommendations involving the storage of grain in buildings with a history of CIPC use and for remedial strategies for decontamination of these buildings