Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil

A simple residue analytical method using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure for the determination of trifloxystrobin and its metabolite trifloxystrobin acid (CGA321113) in tomato and soil was developed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of detection were 0.0005 mg/kg for trifloxystrobin and 0.001 mg/kg for trifloxystrobin acid, respectively. The average recoveries in tomato and soil ranged from 73–99 % for trifloxystrobin and 75–109 % for trifloxystrobin acid, with relative standard deviations below 15 %. The method was then used to study the dissipation and residues in tomato and soil. The dissipation half-lives of trifloxystrobin in tomato were 2.9 days (Beijing) and 5.4 days (Shandong), while in soil were 1.9 days (Beijing) and 3.0 days (Shandong), respectively. The final results showed that the major residue compound was trifloxystrobin in tomato whereas it was its metabolite, trifloxystrobin acid, in soil. The final residues of total trifloxystrobin (including trifloxystrobin acid) were below the EU maximum residue limit of 0.5 mg kg^?1 in tomato 3 days after the treatment.     

Dissipation and residue of famoxadone in grape and soil

The analytical method of famoxadone residue and its dissipation in grape and soil were investigated. Famoxadone (68.75% water-dispersible granule) was applied at two dosages (1.25 and 2.5 g l^???1). Soil and grape samples were collected at intervals and analyzed for famoxadone residues. The results showed that the degradation rate of famoxadone in grape and soil were similar, and their dynamics could be described by C?=?1.1738e ^???0.0562t with correlation coefficient r?=?0.9044 in grape and C?=?5.6565e ^???0.0515t with r?=?0.9620 in soil, respectively. Half-lives were 12.3 and 13.5 days in grape and soil, respectively. The results indicated that at harvest time, the residues of famoxadone in grape were well below the EU’s maximum residue level (2 mg kg^???1) and was safe to apply in grape.     

Dissipation and residue of metalaxyl and cymoxanil in pepper and soil

A simple and accurate method of determining metalaxyl and cymoxanil in pepper and soil was developed by ultra-performance liquid chromatography–photodiode array detection. The limits of detection were 0.015 mg/kg for metalaxyl and 0.003 mg/kg for cymoxanil. The limits of quantification were 0.05 mg/kg for metalaxyl in pepper and soil as well as 0.01 mg/kg for cymoxanil in pepper and soil. Recoveries of pepper and soil were investigated at three spiking levels and ranged within 77.52 to 102.05 % for metalaxyl and 87.15 to 103.21 % for cymoxanil, with relative standard deviations below 9.30 %. For field experiments, the half-lives of metalaxyl were 3.2 to 3.9 days in pepper and 4.4 to 9.5 days in soil at the three experimental locations in China. At harvest, pepper samples were found to contain metalaxyl and cymoxanil well below the maximum residue limit MRLs of the European Union (EU) following the recommended dosage and the interval of 21 days after last application.     

Persistence and Dissipation Kinetics of Spiromesifen in Chili and Cotton

In a field study carried out at three different locations, the dissipation of spiromesifen on cotton and chili was studied and its DT₅₀, and DT₉₉ were estimated at each location. Spiromesifen was sprayed on chili at 96 and 192 g a.i. ha⁻¹ and cotton at 120 and 240 g a.i. ha⁻¹. Samples of chili fruits were drawn at 0, 1, 3, 5, 7, 10, 15, 21, 30 days after treatment and that of cotton seed and lint at first picking and harvest. Soil samples were drawn 30 days after treatment from 0 to 15 and 15 to 30 cm layer. Quantification of residues was done on GC–MS in Selected Ion Monitoring (SIM) mode in mass range 271–274 m/z. The LOQ of this method was found 0.033 μg g⁻¹, LOD being 0.01 μg g⁻¹. The DT₅₀ of spiromesifen when applied at recommended doses in chili fruits was found to be 2.18–2.40 days. Ninety-nine percent degradation was found to occur within 14.5–16.3 days after application. Residues of spiromesifen were not detected in cotton seed and lint samples at the first picking. In soil, no residues of spiromesifen were detectable 15 days after treatment.     

Physicochemical and microbiological assessment of recreational and drinking waters

The present study was aimed to make an assessment of health risk due to pollution and human pathogenic bacteria associated with the recreational and drinking water sources in twin densely populated holy Indian cities Ayodhya and Faizabad. Though physicochemical studies revealed that the water available in the area is under recommended limits for human use, it is unsafe on account of poor microbiological quality of surface and ground water in the region. The most probable number (MPN) test results revealed the preponderance of ≥2,400 total coliforms (TC) (100 ml)^− 1 in river, pond, dug well and kund waters. Contrary to that, 94% tube wells, 32% hand pumps and 25% piped supply water were under safe limits having <3 TC (100 ml)^− 1. The shallow depth (~40 ft), water logging and presence of septic tanks in the near vicinity are the possible reasons of poor microbial quality of hand pump drinking water. The municipal supply water passes along sewage line where loose connections and/or cracks in pipe lead to mixing and contamination. The significant best quality of tube well water evident from the absence of TC could be attributed to the depth of well ≥150 ft and usually their location away from the habitation. A total of 263 bacteria from 186 water samples were isolated, and at least five genera of enteric bacteria from various water sources were identified morphologically and biochemically as Escherichia coli, Klebsiella sp., Enterobacter sp., Shigella sp. and Salmonella sp. The serotyping of 72 E. coli and 36 Salmonella sp. revealed 51 as E. coli O157 and 20 as Salmonella sp. The presence of enteric pathogens in water sources pose threat to human health and therefore call for immediate remedial measures.     

Organochlorines and selenium in California night-heron and egret eggs

Exceptionally high concentrations of DDE were found in black-crowned night-heron (Nycticorax nycticorax) (geometric mean 8.62 g g^–1 wet wt.) and great egret (Casmerodius albus) (24.0 g g^–1) eggs collected from the Imperial Valley (Salton Sea), California in 1985. DDE concentrations in 14 of the 87 (16%) randomly selected night-heron eggs from six colonies (two in San Francisco Bay, three in the San Joaquin Valley, and one at Salton Sea) were higher than those associated with reduced reproductive success of night-herons (8 g g^–1). In addition, mean shell thickness of night-heron eggs collected from the San Joaquin Valley and from San Francisco Bay during 1982–1984 was significantly less than pre-DDT thickness and was negatively correlated (r=–0.50, n=75, P<0.0001) with DDE concentration. Mean selenium concentration in night-heron eggs from Salton Sea (1.10 g g^–1) was significantly higher than in eggs from three locations in the San Joaquin Valley, and in egret eggs from Salton Sea.     

The decline and residues of hexaconazole in tomato and soil

The decline and terminal residues of hexaconazole in tomato and soil in open field were studied. Hexaconazole residues were determined by gas chromatography coupled with an electron capture detector. Recoveries were between 89% and 110% with RSD of 2.99–5.88% in tomato and 90–119% with RSD of 1.15–5.76% in soil at spiked levels of 0.01, 0.1, and 1 mg/kg, respectively. The limit of detection of hexaconazole was 6.3 × 10⁻¹² g. The decline rates of hexaconazole were described using first-order kinetics and the mean half-lives of hexaconazole in tomato and soil were 4.3 and 18.1 days, respectively. The terminal residues in tomato at interval of 7 days at the dosage of 150 g.a.i./hm² for three or four times were all below 0.1 mg/kg. This work would be the guidance of establishing the maximum residue limit of hexaconazole in tomato in China.     

Determination and study on dissipation and residue of bismerthiazol and its metabolite in Chinese cabbage and soil

A simple and accurate method for the determination of bismerthiazol and its metabolite 2-amino-5-mercapto-1,3,4-thiadiazole was developed in Chinese cabbage and soil by high-performance liquid chromatography-diode array detection in this study. The limits of detection were 0.06 mg/kg for bismerthiazol and 0.03 mg/kg for 2-amino-5-mercapto-1,3,4-thiadiazole, respectively. Recoveries of cabbage and soil were investigated at three spiking levels and were in the range of 84.0–96.0 % for bismerthiazol and 71.0–74.6 % for 2-amino-5-mercapto-1,3,4-thiadiazole, with relative standard deviations below 7.0 %. For field experiments, the half-life of bismerthiazol was 2.4–2.5 days in Chinese cabbage and 2.5–4.8 days in soil at the two experimental locations in China. Dissipation residues of 2-amino-5-mercapto-1,3,4-thiadiazole were lower than 0.72 mg/kg. Terminal residues of bismerthiazol and its metabolite were less than 3.0 and 0.3 mg/kg in Chinese cabbage, respectively. No bismerthiazol or metabolite residues were detected in soil on days 5, 7, 10, and 14 after the last spraying at the two dosage levels.     

A Global Model Tracking Water, Nitrogen, and Land Inputs and Virtual Transfers from Industrialized Meat Production and Trade

Rising populations and incomes throughout the world have boosted meat demand by over 75% in the last 20years, intensifying pressures on production systems and the natural resources to which they are linked. As a growing proportion of global meat production is traded, the environmental impacts of production become increasingly separated from where the meat is consumed. In this paper, we quantify the use of three important resources associated with industrial livestock production and trade—water, land, and nitrogen—using a country-specific model that combines trade, agronomic, biogeochemical, and hydrological data. Our model focuses on pigs and chickens, as these animals are raised predominantly in intensive systems using concentrated, compound feeds. The results describe the geographical patterns of environmental resource use due to meat production, trade, and consumption. We show that US feed, animal, and meat destined for export require almost as much nitrogen and land, and 20% more water, than products destined for domestic consumption. Model results also demonstrate that among various production factors, improvements in crop yields and animal feed conversion efficiencies result in the most significant reductions in environmental harm. By explicitly tracking the externalities of meat production, we hope to bolster suppliers’ accountability and provide better information to meat consumers.

溪源水库蓄水前后冬春季水体营养盐和浮游植物特征研究

于2007—2008年溪源水库蓄水前,2014—2015年溪源水库蓄水后对溪源宫水源地水体进行采样,分析了冬春季水体的理化指标、浮游植物生物量及群落组成。蓄水前共鉴定出浮游植物6门26属43种,水体水质状况较好,浮游植物细胞密度平均为7.31×10~5cells/L,以硅藻、绿藻门为优势门类,两者占浮游植物总生物量的比例约为54.7%、32.2%,水体呈贫-中营养状态。蓄水后,水体氮、磷营养盐浓度分别约为蓄水前的2.4倍、3倍,浮游植物细胞密度平均为1.42×10~7cells/L,约为蓄水前的20倍,且群落结构发生改变,优势门类为硅藻、蓝藻、绿藻,所占比例分别为40.2%、38.7%、14.4%,蓝藻门比例有显著提高,约为蓄水前的5倍。说明建库蓄水对浮游植物的影响显著。     

Facile and Sensitive Spectrophotometric Determination of Carbosulfan in Formulations and Environmental Samples

Facile, selective and sensitive spectrophotometric method has been developed for the determination of carbosulfan in insecticidal formulations, fortified water, food grains, agriculture wastewater and soil samples with newly synthesized reagents. The method was based on acid and alkaline hydrolysis of the carbosulfan pesticide, and the resultant hydrolysis product of carbosulfan was coupled with 2,6-dibromo-4-methylaniline to give a yellow color product with λ _max of 464 nm or interaction with 2,6-dibromo-4-nitroaniline to produce yellow colored product with λ _max of 408 nm or coupling with 2,4,6-tribromoaniline to form red colored product has a λ _max of 471 nm. Under optimal conditions, Beer’s law range for 2,6-dibromo-4-methylaniline (DBMA) was found to be 0.2–12.0 μg ml⁻¹, 0.6–16.0 μg ml⁻¹ for 2,6-dibromo-4-nitroaniline (DBNA) and 0.4–15.0 μg ml⁻¹ for 2,4,6-tribromoaniline (TBA). The molar absorptivity of the color systems were found to be 3.112 × 10⁴ l mol⁻¹ cm⁻¹ for DBMA, 3.214 × 10⁴ l mol⁻¹ cm⁻¹ for DBNA and 3.881 × 10⁴ l mol⁻¹ cm⁻¹ for TBA. Sandell’s of the color reactions are 0.013 μg cm⁻² (DBMA), 0.012 μg cm⁻² (DBNA) and 0.011 μg cm⁻² (TBA) respectively. The effect of the non-target species on the determination of carbosulfan was studied to enhance the selectivity of the proposed methods. The formation of colored derivatives with the coupling agents is instantaneous and stable for 28, 30, and 26 h. Performance of the proposed methods were compared statistically in terms Student’s F and t-tests with the reported methods. An erratum to this article can be found at     

Losses of nitrogen and phosphorus from agricultural and forest areas in Finland during the 1980s and 1990s

The temporal changes and spatial variability of phosphorus andnitrogen losses and concentrations in Finland during the period1981–1997 were studied in 15 small agricultural and forestedcatchments. In addition, four coastal river basins with highagricultural land use located in southern Finland were includedin the study in order to assess the representativeness ofagricultural loss estimates from small agricultural catchments.The mean annual loss specific for agricultural land was estimatedto be on average 110 kg km^-2 a^-1 for total phosphorusand 1500 kg km^-2 a^-1 for total nitrogen. The resultsfrom small agricultural catchments were in agreement with thecorresponding loss estimates from rivers, with an average of137 kg km^-2 a^-1 for total phosphorus and 1800 kg km^-2a^-1 for total nitrogen. The results from the studiedagricultural catchments and rivers during the period 1981–1997suggest that weather-driven fluctuation in discharge was usuallythe main reason for changes in nutrient losses, and little or noimpact of changes in agricultural production or managementpractises can be observed. In forested areas the total phosphorusloss (average 9 kg km^-2 a^-1) and total nitrogen loss(average 250 kg km^-2 a^-1) were lower than inagricultural areas. In forested catchments the impact of forestryoperations, such as clear-cutting and fertilization, and theimpact of atmospheric nitrogen deposition can be seen in changesin nutrient losses.     

Dissipation and residue behavior of mepiquat on wheat and potato field application

A modified LC-MS method for the analysis of mepiquat residue in wheat, potato, and soil was developed and validated. A hydrophilic interaction liquid chromatographic column has been successfully used to retain and separate the mepiquat. Mepiquat residue dynamics and final residues in supervised field trials at Good Agricultural Practice (GAP) conditions in wheat, potato, and soil were studied. The limits of quantification for mepiquat in all samples were all 0.007 mg kg^?1, which were lower than their maximum residue limits. At fortification levels of 0.04, 0.2, and 2 mg kg^?1 in all samples, recoveries ranged from 77.5 to 116.4 % with relative standard deviations of 0.4–7.9 % (n?=?5). The dissipation half-lives (T _1/2) of mepiquat in soil (wheat), wheat plants, soil (potato), and potato plants were 4.5–6.3, 3.0–5.6, 2.2–4.6, and 2.4–3.2 days, respectively. The final residues of mepiquat were below 0.153 mg kg^?1 in soil (wheat), 0.052–1.900 mg kg^?1 in wheat, below 0.072 mg kg^?1 in soil (potato), and below 1.173 mg kg^?1 in potato at harvest time. Moreover, pesticide risk assessment for all the detected residues was conducted. A maximum 0.0012 % of acceptable daily intake (150 mg kg^?1) for national estimated daily intake indicated low dietary risk of these products.     

Understanding and eliminating iron interference in colorimetric nitrate and nitrite analysis

Across many environments, nitrate ( $\mbox{NO}_{3}^-$ ) is an important form of N available for microorganisms and photosynthetic organisms. Accurate $\mbox{NO}_{3}^-$ measurements are important for examining N cycling and retention in terrestrial and aquatic ecosystems, but a common method of $\mbox{NO}_{3}^-$ analysis can underestimate $\mbox{NO}_{3}^-$ concentrations when soluble iron is present (iron > 10 mg L^???1). The basic method is robust, using copperized cadmium to reduce $\mbox{NO}_{3}^-$ and then diazotizing the resulting $\mbox{NO}_{2}^-$ in a two-step process to form an easily measured colored product. We show that iron interference is unique to using an NH₄Cl and ethylenediaminetetraacetic acid (EDTA) buffer. We hypothesize that interference is through iron-catalyzed reduction of the intermediate color product, a diazonium ion. We examine three historical buffers as alternatives to NH₄Cl/EDTA and recommend replacement of EDTA with diethylenetriaminepentaacetic acid, which chelates metals much like EDTA, but unlike EDTA, it does not cause interference in the presence of iron.     

Fuel characteristics and emissions from biomass burning and land-use change in Nigeria

Nigeria is one of the 13 low-latitude countries that have significant biomass burning activities. Biomass burning occurs in moist savanna, dry forests, and forest plantations. Fires in the forest zone are associated with slash-and-burn agriculture; the areal extent of burning is estimated to be 80% of the natural savanna. In forest plantations, close to 100% of litter is burned. Current estimates of emissions from land-use change are based on a 1976 national study and extrapolations from it. The following non-carbon dioxide (CO₂) trace gas emissions were calculated from savanna burning: methane (CH₄), 145 gigagrams (Gg); carbon monoxide (CO), 3831 Gg; nitrous oxide (N₂O), 2 Gg; and nitrogen oxides (NO_x), 49 Gg. Deforestation rates in forests and woodlands are 300 × 10³ ha (kilohectare, or kha) and 200 × kha per year, respectively. Trace gas emissions from deforestation were estimated to be 300 Gg CH₄, 2.4 Gg N₂O, and 24 Gg NO_x. CO₂ emissions from burning, decay of biomass, and long-term emissions from soil totaled 125 561 Gg. These estimates should be viewed as preliminary, because greenhouse gas emission inventories from burning, deforestation, and land-use change require two components: fuel load and emission factors. Fuel load is dependent on the areal extent of various land uses, and the biomass stocking and some of these data in Nigeria are highly uncertain.     

Dissipation and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Dissipation and residue of triforine in strawberry and soil

Two independent field trials were performed in Guangdong and Hubei, China in 2011 to investigate the dissipation and residue levels of triforine in strawberry and soil. A fast and simple method using gas chromatography with electron capture detector was developed and validated to determine triforine levels in strawberry and soil. The average recovery of triforine in strawberry ranged from 87.46 to 104.32 % with a relative standard deviation (RSD) of 0.72 to 4.54 %; that in soil ranged from 83.82 to 103.01 % with an RSD of 3.89 to 4.36 %. The limit of quantification of the proposed method was 0.01 mg/kg for both strawberry and soil. The results suggest that the triforine dissipation curves followed the first-order kinetic. The half-lives of triforine in strawberry from Guangdong and Hubei were 3.58 and 4.42 days, respectively; those in soil were 3.53 and 4.10 days, respectively. The terminal residues of triforine in strawberry ranged from 0.032 to 0.264 mg/kg at preharvest intervals of 0.5, 1, and 3 days. These values are lower than the maximum residue limit of 1 mg/kg in strawberry set by the Codex Alimentarius Commission.     

Profiling and monitoring of DOM in brewery wastewater and treated wastewater

Dissolved organic matter (DOM) in raw and treated wastewater from two breweries in Thailand was profiled and monitored for the purpose of water reclamation. The wastewater and the effluent from the use of an upflow anaerobic sludge blanket (UASB) and activated sludge (AS) were collected and analyzed through a resin fractionation method using the fluorescent excitation?Cemission matrix (FEEM) technique. The results revealed that the major organic fractions in the brewery wastewater were hydrophobic acid (HPOA) and hydrophilic base (HPIB), accounting for 65% of total dissolved organic carbon (DOC) mass for brewery A and 56% of total DOC mass for brewery B. The FEEM results indicated that the organic matter in the wastewaters of both breweries were mainly composed of tryptophan-like substances, represented by peaks C (230 nm_Ex/340?C365 nm_Em) and D (265?C295 nm_Ex/315?C390 nm_Em), and humic-like substances, represented by peaks E (290 nm_Ex/400 nm_Em), F (330?C335 nm_Ex/395?C410 nm_Em), and G (255?C265 nm_Ex/435?C455 nm_Em). The analysis revealed that the reduction of DOM occurred mostly during the UASB treatment where most of the DOM reduction resulted from the removal of the HPOA and HPIB fractions. The HPOA fraction, a group of humic-like substances, is of particular concern when reclaiming treated brewery wastewater, and although it was reduced by more than 80% of its initial amount, it was still a dominant DOM fraction in the effluents.     

Macro- and microelement distribution in organs of Glyceria maxima and biomonitoring applications

The content of nutrients (N, P, K, Ca and Mg) and of trace metals (Fe, Cu, Mn, Zn, Pb, Cd, Co and Ni) in water, bottom sediments and various organs of Glyceria maxima from 19 study sites selected in the Jeziorka River was determined. In general, the concentrations of nutrients recorded in the plant material decreased in the following order: leaf>root>rhizome>stem, while the concentrations of the trace elements showed the following accumulation scheme: root>rhizome>leaf>stem. The bioaccumulation and transfer factors for nutrients were significantly higher than for trace metals. G. maxima from agricultural fields was characterised by the highest P and K concentrations in leaves, and plants from forested land contained high Zn and Ni amounts. However, the manna grass from small localities showed high accumulation of Ca, Mg and Mn. Positive significant correlations between Fe, Cu, Zn, Cd, Co and Ni concentrations in water or sediments and their concentrations in plant indicate that G. maxima may be employed as a biomonitor of trace element contamination. Moreover, a high degree of similarity was noted between self-organizing feature map (SOFM)-grouped sites of comparable quantities of elements in the water and sediments and sites where G. maxima had a corresponding content of the same elements in its leaves. Therefore, SOFM could be recommended in analysing ecological conditions of the environment from the perspective of nutrients and trace element content in different plant species and their surroundings.     

Temporal variability in nutrient concentrations and loads in the River Tamar and its catchment (SW England) between 1974 and 2004

This study reports the results from the analyses of a 30-year (1974–2004) river water quality monitoring dataset for NO _x –N (NO₃–N?+?NO₂–N), NH₄–N, PO₄–P and SiO₂–Si at the tidal limit of the River Tamar (SW England), an agriculturally dominated and sparsely populated catchment. Annual mean concentrations of NH₄–N, PO₄–P and SiO₂–Si were similar to other rural UK rivers, while annual mean concentrations of NO _x –N were clearly lower. Estimated values for the 1940s were much lower than for those of post-1974, at least for NO₃–N and PO₄–P. Flow-weighted mean concentrations of PO₄–P decreased by approximately 60 % between 1974 and 2004, although this change cannot be unequivocally ascribed to either PO₄–P stripping from sewage treatment work effluents or reductions in phosphate fertiliser applications. Lower-resolution sampling (to once per month) in the late 1990s may also have led to the apparent decline; a similar trend was also seen for NH₄–N. There were no temporal trends in the mean concentrations of NO _x –N, emphasising the continuing difficulty in controlling diffuse pollution from agriculture. Concentrations of SiO₂–Si and NO _x –N were significantly and positively correlated with river flows ≤15 m³?s^?1, showing that diffuse inputs from the catchment were important, particularly during the wet winter periods. In contrast, concentrations of PO₄–P and NH₄–N did not correlate across any flow window, despite the apparent importance of diffuse inputs for these constituents. This observation, coupled with the absence of a seasonal (monthly) cycle for these nutrients, indicates that, for PO₄–P and NH₄–N, there were no dominant sources and/or both undergo extensive within-catchment processing. Analyses of nutrient fluxes reveal net losses for NO₃–N and SiO₂–Si during the non-winter months; for NO₃–N, this may be due to denitrification. Areal fluxes of NO _x –N from the catchment were towards the higher end of the range for the UK, while NH₄–N and PO₄–P were closer to the lower end of the ranges for these nutrients. These data, taken together with information on sestonic chlorophyll a, suggest that water quality in the lower River Tamar is satisfactory with respect to nutrients. Analyses of these monitoring data, which were collected at considerable logistical and monetary cost, have revealed unique insights into the environmental behaviour of key nutrients within the Tamar catchment over a 30-year period.