Organic contaminants in imported salmon feed and their effects on reef ecosystems in New Zealand.

Organic matter from salmon farms has been shown to be assimilated by soft sediment and rocky reef communities within the ecological footprint of salmon farms. Given these findings, another question arises - What other chemicals in salmon feed may be assimilated into wild communities via organic waste from salmon farms? Here we measured a suite of organic contaminants in salmon feed, in organisms used in a controlled feeding experiment, and in reef species collected within the depositional footprint of salmon farms. Gas Chromatography-Tandem Mass Spectrometry was used to quantify trace concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and current-use (CPUs) and historic-use pesticides (HUPs) in salmon feed imported to New Zealand. The effect of assimilation of farm-derived organic matter on contaminant profiles differed among species during the controlled feeding experiment and demonstrated that migration of individuals to a farm-associated site has the potential to increase or decrease organic contaminant concentrations. Concentrations of PCBs in Parapercis colias (blue cod), a highly resident, long-lived fish, were significantly higher at farm sites than at reference sites. While these concentrations were relatively low in a global context, this result presents blue cod as an important candidate for future monitoring of organic contaminants around point sources. PCBs and PBDEs measured in wild marine species were all below limits set by the European Union, whereas concentrations of certain HUPs, specifically dichlorodiphenyltrichloroethane (DDT) and its degradation products and endosulfan, may be of concern as a consequence of alternative anthropogenic activities. Overall, feed imported to New Zealand had relatively low levels of most organic contaminants that, at current levels, are unlikely to result in significant ecological effects to wild communities in adjacent habitats.

Real-Time Measurement of Herbicides in the Atmosphere: A Case Study of MCPA and 2,4-D during Field Application.

Atmospheric sources of herbicides enable short- and long-range transport of these compounds to off-target areas but the concentrations and mechanisms are poorly understood due, in part, to the challenge of detecting these compounds in the atmosphere. We present chemical ionization time-of-flight mass spectrometry as a sensitive, real-time technique to detect chlorinated phenoxy acid herbicides in the atmosphere, using measurements during and after application over a field at Colorado State University as a case study. Gas-phase 2,4-dichlorophenoxyacetic acid (2,4-D) mixing ratios were greatest during application (up to 20 pptv), consistent with rapid volatilization from spray droplets. In contrast, atmospheric concentrations of 2-methyl-4-chlorophenoxyacetic acid (MCPA) increased for several hours after the initial application, indicative of a slower source than 2,4-D. The maximum observed gas-phase MCPA was 60 pptv, consistent with a post-application volatilization source to the atmosphere. Exposure to applied pesticides in the gas-phase can thus occur both during and at least several hours after application. Spray droplet volatilization and direct volatilization from surfaces may both contribute pesticides to the atmosphere, enabling pesticide transport to off-target and remote regions.

Atmospheric OH oxidation chemistry of trifluralin and acetochlor.

Trifluralin and acetochlor are two nitrogen-containing current use herbicides. While both herbicides have been observed in the atmosphere and have the potential to undergo atmospheric oxidation before deposition to off-target areas, the atmospheric photooxidation chemistry of these species is poorly understood. We use an oxidative flow reactor to expose the two herbicides to increasing concentrations of OH radicals, detecting pesticides and products using an iodide chemical ionization mass spectrometer. We identify new oxidation products and propose photooxidation mechanisms for trifluralin and acetochlor. Both herbicides contain reduced organic nitrogen atoms, and their OH oxidation produces isocyanic acid. While aerosol was observed in the flow reactor only for acetochlor, our results indicate that OH oxidation of neither herbicide would contribute to secondary organic aerosol formation under typical ambient atmospheric conditions. However, high wall losses of both pesticides in the flow reactor suggests that partitioning to pre-existing aerosol may occur and enable subsequent transport in the atmosphere.

Atmospheric OH Oxidation of Three Chlorinated Aromatic Herbicides.

Chlorinated phenoxy acids are a widely used class of herbicides and have been found in remote regions far from sources. However, the atmospheric chemistry of these compounds is poorly understood. We use an oxidative flow reactor coupled to chemical ionization mass spectrometry to investigate OH oxidation of two chlorinated phenoxyacid herbicides (2-methyl-4-chlorophenoxyacetic acid (MCPA) and mecoprop-p) and one chlorinated pyridine herbicide (triclopyr). OH radicals add to the aromatic rings of the three herbicides, produce peroxides via hydrogen abstraction, or fragment at the ether bond. OH oxidation of MCPA produced two potentially toxic compounds: chlorosalicylaldehyde and chlorosalicylic acid. We use standards to validate the detection of these oxidation products by acetate CIMS and quantify the reaction rate. Oxidation of triclopyr produced a known endocrine disruptor, 3,5,6-trichloro-2-pyridinol. Thus, while some OH oxidation products are less toxic than the parent molecules (e.g., C1-5 carboxylic acids), others may be as or more toxic than the parent herbicide. We determine effective rate coefficients for OH addition to the aromatic ring ( kOH) for mecoprop-p of 1.5 (±0.7) × 10-12 cm3 molecules-1 s-1 and for MCPA of 2.6 (±0.3) × 10-12 cm3 molecules-1 s-1. The atmospheric lifetimes with respect to OH are thus long enough that photochemistry may be relevant to the environmental fate of these pesticides.