Capturing temporal variability for estimates of annual hydrochemical export from a first‐order agricultural catchment in southern Ontario,Canada

This 2‐year study (2000, 2001) reports annual nutrient (phosphorus, nitrate) export from a first‐order agricultural watershed in southern Ontario based on an intensive monitoring programme. The importance of storm and melt events in annual export estimates is demonstrated and the temporal variability in nutrient loading during events is related to processes occurring within the catchment. The feasibility of predicting event‐related nutrient export from hydrometric data is explored. The importance of sampling frequency throughout events is also shown. Export of total phosphorus (TP), soluble reactive phosphorus (SRP) and nitrate ( ) for 2000 and 2001 averaged 0·35 kg ha^?1 year^?1, 0·09 kg ha^?1 year^?1, and 35 kg ha^?1 year^?1 (as N) respectively. Approximately 75% of annual TP export, 80% of annual SRP export and 70% of annual export occurred during 28 events per year. A small number of large‐magnitude events (>34 mm) accounted for 18–42% of annual TP export, 0–61% of annual SRP export and 13–33% of annual NO export. Our results show that temporal variability in nutrient export is largely governed by discharge in this basin, and export can be predicted from discharge. SRP and TP export can also be predicted from discharge, but only for events that are not large in magnitude. The sampling interval throughout events is important in obtaining precise estimates of nutrient export, as infrequent sampling intervals may over‐ or under‐estimate nutrient export by ± 45% per event for P. This study improves our understanding of and P export patterns and our ability to predict or model them by relating temporal variability in event nutrient export to discharge and processes occurring within the basin, and also by exploring the significance of sampling interval in the context of the importance of individual events, season and temporal variability during events. Copyright © 2006 John Wiley & Sons, Ltd.     

Precipitation of heavy metals in produced water: influence on contaminant transport and toxicity

Produced water undergoes changes in its physical chemistry including precipitation of heavy metals after being discharged and mixed with ambient seawater. Potential impacts of the precipitation of heavy metals on their transport and toxicity were studied using samples from offshore oil production sites on the Scotian Shelf off eastern Canada. Concentrations of aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel and zinc were measured in total, particulate and dissolved fractions together with Microtox tests for assessment of toxicity. Heavy metals in produced water were transformed from dissolved to particulate phase in a period of hours under oxygenated conditions, and aggregated to larger particles that settle rapidly (>100 m/day) over a few days. In addition, there was production of buoyant particles comprised of heavy metal precipitates sequestered onto oil droplets that were transported to the surface. The particulate fraction was generally more toxic than the dissolved fraction. This was evident at the mixing interface between produced water and seawater where elevated particulate and toxicity levels were observed. Laboratory studies suggest an increase in the toxicity of discharged produced water over time. Time-series experiments showed a sustained toxic response for more than a week following the oxidation of freshly discharged produced water that initially elicited little or no toxic response in the Microtox test. Chemical processes identified in this study, namely precipitation of heavy metals and consequent settling and rising fluxes of particles, will influence the toxicity, the fate and the transport of potential contaminants in the produced water. Therefore, these processes need to be considered in assessment of the environmental impact associated with offshore oil and gas operations.     

Measurement of nitric oxide in the stratosphere between 17·4 and 22·9 km

On 16 March 1973, the York U./U.S.U. chemiluminescent nitric oxide instrument was flown successfully from Hollomon Air Force Base, New Mexico, 32° 50·1′ N lat. The instrument was operated between 17:40 and 22:05UT. Most of the measurements were carried out during three ascent, float and descent cycles between 17·4 and 22·9 km. Within the uncertainty of the measurements no differences were seen among results obtained during ascent, float and descent mode, which indicated that there were no major sampling problems resulting from contamination of the atmosphere. The NO mixing ratio was found to be 0·1 ppb v/v with an accuracy of 60 per cent. No change was observed within this accuracy over the small altitude range investigated.     

Provenances of naturalised plants in Australasia

In both Australia and New Zealand, numbers of naturalised flowering plant species have increased steadily since the start of European settlement, and this process shows no sign of abating. Plants native to Western Europe, the Mediterranean basin and the Middle East predominated during the mid‐nineteenth century, but in recent decades other geographical areas (notably the Western Hemisphere, Asia and Southern Africa) have become important sources of adventive plants. Today, the composition of ensembles of naturalised species more closely conforms to the diversity of physical environments in the host area. Species native to mediterranean‐type climates tend to dominate in Victoria, species from the Asian and American tropics are especially significant in Queensland, and species from cool temperate regions compose the bulk of the naturalised flora of south‐western New Zealand.     

N/N and O/O stable isotope ratios of nitrous oxide produced during denitrification in temperate forest soils

Anaerobic incubations of upland and wetland temperate forest soils from the same watershed were conducted under different moisture and temperature conditions. Rates of nitrous oxide (N₂O) production by denitrification of nitrate () and the stable isotopic composition of the N₂O (δ¹⁵N, δ¹⁸O) were measured. In all soils, N₂O production increased with elevated temperature and soil moisture. At each temperature and moisture level, the rate of N₂O production in the wetland soil was greater than in the upland soil. The ¹⁵N isotope effect (ε) _{(product − substrate)} ranged from −20‰ to −29‰. These results are consistent with other published estimates of ¹⁵N fractionation from both single species culture experiments and soil incubation studies from different ecosystems.A series of incubations were conducted with ¹⁸O-enriched water (H₂O) to determine if significant oxygen exchange (O-exchange) occurred between H₂O and N₂O precursors during denitrification. The exchange of H₂O-O with nitrite () and/or nitric oxide (NO) oxygen has been documented in single organism culture studies but has not been demonstrated in soils prior to this study. The fraction of N₂O-O derived from H₂O-O was confined to a strikingly narrow range that differed between soil types. H₂O-O incorporation into N₂O produced from upland and wetland soils was 86% to 94% and 64% to 70%, respectively. Neither the temperature, soil moisture, nor the rate of N₂O production influenced the magnitude of O-exchange. With the exception of one treatment, the net ¹⁸O isotope effect (ε_net) _{(product-substrate)} ranged from +37‰ to +43‰.Most previous studies that have reported ¹⁸O isotope effects for denitrification of to N₂O have failed to account for the effect of oxygen exchange with H₂O. When high amounts of O-exchange occur after fractionation during reductive O-loss, the ¹⁸O-enrichment is effectively lost or diminished and δ¹⁸O-N₂O values will be largely dictated by δ¹⁸O-H₂O values and subsequent fractionation. The process and extent of O-exchange, combined with the magnitude of oxygen isotope fractionation at each reduction step, appear to be the dominant controls on the observed oxygen isotope effect. In these experiments, significant oxygen isotope fractionation was observed to occur after the majority of water O-exchange. Due to the importance of O-exchange, the net oxygen isotope effect for N₂O production in soils can only be determined using δ¹⁸O-H₂O addition experiments with δ¹⁸O-H₂O close to natural abundance.The results of this study support the continued use of δ¹⁵N-N₂O analysis to fingerprint N₂O produced from the denitrification of . The utilization of ¹⁸O/¹⁶O ratios of N₂O to study N₂O production pathways in soil environments is complicated by oxygen exchange with water, which is not usually quantified in field studies. The oxygen isotope fractionation observed in this study was confined to a narrow range, and there was a clear difference in water O-exchange between soil types regardless of temperature, soil moisture, and N₂O production rate. This suggests that ¹⁸O/¹⁶O ratios of N₂O may be useful in characterizing the actively denitrifying microbial community.     

Agents of landscape change in southern New Zealand, 1896–1920

The records of two large stock and station agents, Loan & Mercantile Agency in Dunedin and Wright Stephenson in Invercargill, allowed us to track the timing, nature, magnitude and rate of landscape change in southern New Zealand between 1896 and 1920. This period extends from the final years of subdivision of large estates, and includes closer settlement, the shift from pastoral farming to intensive agriculture, growth of dairying, and increasing mechanisation of agriculture. These changes are reflected in clients’ annual expenditures on capital items such as fencing and building materials, tools and implements, materials for drains.     

Extent and magnitude of copper contamination in marinas of the San Diego region, California, USA

Marinas are areas of special water quality concern because of the potential for pollutant accumulation within their protected waters. Perhaps the largest contaminant source to marinas is antifouling paints that leach copper to prevent the growth of encrusting organisms on vessel bottoms. Very little monitoring of marinas is typically conducted despite the potential environmental risk, particularly in the San Diego region of California, USA where as many as 17,000 recreational vessels are berthed. The objective of this study was twofold: (1) determine the extent and magnitude of dissolved copper concentrations in marinas throughout the San Diego region, and (2) determine if elevated copper concentrations in marinas of the San Diego region are resulting in adverse biological impacts. A probabilistic study design was used to sample water column copper concentrations and toxicity (using Mytilus galloprovincialis) at 30 stations. Results indicated that exceedence of state water quality objectives was widespread (86% of marina area), but that toxicity was much less prevalent (21% of marina area). Toxicity identification evaluations (TIEs) conducted at the most toxic sites indicated that toxicity was largely due to trace metals, most likely copper. Toxicity was reduced using TIE treatments that chelated trace metals such as cation exchange column, ethylenediaminetetraacetic acid (EDTA), and sodium thiosulfate (STS). Moreover, increasing dissolved copper concentrations correlated with increasing toxicity and these copper concentrations were high enough to account for virtually all of the observed toxicity.     

The isotopic composition of nitrate produced from nitrification in a hardwood forest floor

Dual isotopic analysis of nitrate (¹⁵N/¹⁴N and ¹⁸O/¹⁶O) is increasingly used to investigate the environmental impacts of human-induced elevated atmospheric nitrate deposition. In forested ecosystems, the nitrate found in surface water and groundwater can originate from two sources: (1) atmospheric deposition, and (2) nitrate produced from nitrification in forest soils (microbial nitrate). Application of the dual nitrate isotope technique for determining the relative importance of nitrate sources in forested catchments requires knowledge of the isotopic composition of microbial nitrate. We excluded precipitation inputs to three zero-tension lysimeters installed below the F-horizon (Oe) at the Turkey Lakes Watershed (TLW) in order to measure the isotopic composition of microbial nitrate produced in situ. To our knowledge, this is the first in situ study of the isotopic composition of microbial nitrate in forest soils. Over a 2-week period, nitrate produced by nitrification was periodically flushed to the lysimeters by watering the area with a nitrogen-free solution. Nitrate produced in the forest floor had δ¹⁸O values ranging from +3.1‰ to +10.1‰ with a mean of +5.2‰. These values were only slightly higher than from the expected value of +1.0‰ calculated for chemolithoautotrophic nitrification, which depends on the δ¹⁸O of available O₂ and H₂O. In addition to nitrate, we also collected soil gas to determine if soil respiration and O₂ diffusion affected soil gas δ¹⁸O-O₂, which is typically assumed to be identical to atmospheric O₂ (+23.5‰) when calculating microbial nitrate δ¹⁸O values. No significant difference in δ¹⁸O-O₂ from atmospheric O₂ was found in forest soils to a depth of 55 cm, and therefore ¹⁸O-enrichment of soil gas O₂ could not explain the modest enrichment of nitrate ¹⁸O. Evaporative ¹⁸O-enrichment of soil water available to nitrifiers in the forest floor is a plausible mechanism for slightly elevated nitrate δ¹⁸O values. However, the observed nitrate δ¹⁸O values could also be explained by a minor contribution of nitrate from heterotrophic nitrifiers. The δ¹⁵N of nitrate produced ranged from −10.4 to −7.3‰ and, as expected, was depleted in ¹⁵N relative to soil organic nitrogen. Microbial nitrate produced in the forest floor was also significantly depleted in ¹⁵N relative to microbial nitrate exported in groundwater and headwater streams at the TLW. We hypothesize that ¹⁵N-depleted forest floor nitrate is not detected in groundwaters largely because of: (1) the immobilization of forest floor nitrate in the mineral soil and (2) the mixing of the remaining forest floor nitrate with nitrate generated in the mineral soil, which is expected to have higher δ¹⁵N values. This study demonstrates that current methods of calculating a priori the δ¹⁸O of microbial nitrate provide a reasonable value for nitrate produced by nitrification at the TLW.