Abstract:Riverine particulate organic matter (POM) samples were collected bi-weekly to monthly from 40 sites in the Mississippi, Colorado, Rio Grande, and Columbia River Basins (USA) in 1996-97 and analysed for carbon and nitrogen stable isotopic compositions. These isotopic compositions and C : N ratios were used to identify four endmember sources of POM: plankton, fresh terrestrial plant material, aquatic plants, and soil organic material. This large-scale study also incorporated ancillary chemical and hydrologic data to refine and extend the interpretations of POM sources beyond the source characterizations that could be done solely with isotopic and elemental ratios. The ancillary data were especially useful for differentiating between seasonal changes in POM source materials and the effects of local nutrient sources and in-stream biogeochemical processes.Average values of υ 13 C and C : N for all four river systems suggested that plankton is the dominant source of POM in these rivers, with higher percentages of plankton downstream of reservoirs. Although the temporal patterns in some rivers are complex, the low υ 13 C and C : N values in spring and summer probably indicate plankton blooms, whereas relatively elevated values in fall and winter are consistent with greater proportions of decaying aquatic vegetation and/or terrestrial material. Seasonal shifts in the υ 13 C of POM when the C : N remains relatively constant probably indicate changes in the relative rates of photosynthesis and respiration. Periodic inputs of plant detritus are suggested by C : N ratios >15, principally on the Columbia and Ohio Rivers. The υ 15 N and υ 13 C also reflect the importance of internal and external sources of dissolved carbon and nitrogen, and the degree of in-stream processing. Elevated υ 15 N values at some sites probably reflect inputs from sewage and/or animal waste. This information on the spatial and temporal variation in sources of POM in four major river systems should prove useful in future food web and nutrient transport studies.

[1] Snowpack, snowmelt, precipitation, surface water, and groundwater samples from the Loch Vale watershed in Colorado were analyzed for d 15 N and d 18O of nitrate to determine the processes controlling the release of atmospherically deposited nitrogen from alpine and subalpine ecosystems. Although overlap was found between the d 15 N (NO3) values for all water types (À4 to +6%), the d 18 O (NO3) values for surface water and groundwater (+10 to +30%) were usually distinct from snowpack, snowmelt, and rainfall values (+40 to +70%). During snowmelt, d18 O (NO3) indicated that about half of the nitrate in stream water was the product of microbial nitrification; at other times that amount was greater than half. Springs emerging from talus deposits had high nitrate concentrations and a seasonal pattern in d18 O (NO3) that was similar to the pattern in the streams, indicating that shallow groundwater in talus deposits is a likely source of stream water nitrate. Only a few samples of surface water and groundwater collected during early snowmelt and large summer rain events had isotopic compositions that indicated most of the nitrate came directly from atmospheric deposition with no biological assimilation and release. This study demonstrates the value of the nitrate double-isotope technique for determining nitrogencycling processes and sources of nitrate in small, undisturbed watersheds that are enriched with inorganic nitrogen.

To determine whether NO 3 − concentration pulses in surface water in early spring snowmelt discharge are due to atmospheric NO 3 − , we analyzed stream δ 15 N-NO 3 − and δ 18 O-NO 3 − values between February and June of 2001 and 2002 and compared them to those of throughfall, bulk precipitation, snow, and groundwater. Stream total Al, DOC and Si concentrations were used to indicate preferential water flow through the forest floor, mineral soil, and ground water. The study was conducted in a 135-ha subcatchment of the Arbutus Watershed in the Huntington Wildlife Forest in the Adirondack Region of New York State, U.S.A. Stream discharge in 2001 increased from 0.6 before to 32.4 mm day −1 during snowmelt, and element concentrations increased from 33 to 71 µmol L −1 for NO 3 − , 3 to 9 µmol L −1 for total Al, and 330 to 570 µmol L −1 for DOC. Discharge in 2002 was variable, with a maximum of 30 mm day −1 during snowmelt. The highest NO 3 − , Al, and DOC concentrations were 52, 10, and 630 µmol L −1 , respectively, and dissolved Si decreased from 148 µmol L −1 before to 96 µmol L −1 during snowmelt. Values of δ 15 N and δ 18 O of NO 3 − in stream water were similar in both years. Stream water, atmospherically-derived solutions, and groundwaters had overlapping δ 15 N-NO 3 − values. In stream and ground water, δ 18 O-NO 3 − values ranged from +5.9 to +12.9‰ and were significantly lower than the +58.3 to +78.7‰ values in atmospheric solutions. Values of δ 18 O-NO 3 − indicating nitrification, increase in Al and DOC, and decrease in dissolved Si concentrations indicating water flow through the soil suggested a dilution of groundwater NO 3 − by increasing contributions of forest floor and mineral soil NO 3 − during snowmelt.

[1] A seasonal analysis assesing variations in the oxygen isotopic composition of dissolved inorganic phosphate (DIP) was conducted in the San Francisco Bay estuarine system, California. Isotopic fractionation of oxygen in DIP (exchange of oxygen between phosphate and environmental water) at surface water temperatures occurs only as a result of enzyme-mediated, biological reactions. Accordingly, if phospate demand is low relative to input and phosphate is not heavily cycled in the ecosystem, the oxygen isotopic composition of DIP (

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the delta(34)S isotopic composition of plants, animals and soils. We found that the online technology for automated delta(34)S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO(2) produced, and as a result calculated delta(34)S values were often 1-3 per thousand too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO(2)-SiO(2) buffering method that minimizes detrimental oxygen isotope variations in SO(2).