Groundwater and wetlands contamination with pesticides and nutrients from farms in Victoria, Australia

doi:10.21203/rs.3.rs-4361284/v1

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Groundwater and wetlands contamination with pesticides and nutrients from farms in Victoria, Australia

https://doi.org/10.21203/rs.3.rs-4361284/v1

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Intensive farming in regions like the Glenelg Hopkins, Victoria, Australia, leads to substantial usage of pesticides and nutrients, posing the risk of agrochemical pollution to groundwater and wetlands. This study estimates the extent of pollution in aquifers and wetlands in the agricultural region. Tests were conducted for triazines (atrazine, hexazinone, metribuzin, prometrym, simazine, desisopropyl-atrazine, and desethyl-atrazine), nitrogen and phosphorus in 23 groundwater monitoring bores susceptible to agricultural pollution and ten nearby wetlands. Results indicated that one bore exhibited elevated pesticide levels, with a total concentration of 19.43 µg/L. Nitrogen and phosphorus were detected in most groundwater bores with concentrations below 51.6 mg/L and 0.30 mg/L, respectively. Compound Atrazine was found in three wetlands below 0.064 µg/L, while simazine was detected in four wetlands below 1.2 µg/L. The study suggests that although low pesticide levels were observed in wetlands, nutrient contamination is prevalent in the aquifer at the study site. Further investigation is necessary to comprehend the impacts of pesticides and nutrients on groundwater and wetland ecosystems. These findings emphasize the importance of ongoing monitoring and research to mitigate the adverse effects of intensive agricultural practices on groundwater and wetlands, thus, holding significant implications for policymakers and researchers.

Earth and environmental sciences/Environmental sciences/Environmental chemistry/Environmental monitoring

Earth and environmental sciences/Environmental sciences/Environmental chemistry/Geochemistry

Earth and environmental sciences/Environmental sciences/Environmental chemistry/Pollution remediation

Physical sciences/Chemistry/Environmental chemistry/Geochemistry

Physical sciences/Chemistry/Environmental chemistry/Pollution remediation

Earth and environmental sciences/Limnology

Earth and environmental sciences/Solid earth sciences/Geochemistry

Earth and environmental sciences/Environmental sciences/Environmental chemistry

Earth and environmental sciences/Environmental sciences/Environmental impact

Pesticides

nutrients

triazines

contamination

groundwater

wetlands

Water availability is crucial for the productivity of natural and agricultural ecosystems (Nemani et al., 2003), with groundwater quality and quantity being vital for human development and sustaining groundwater-dependent ecosystems (Eamus et al., 2006). In regions like Victoria, Australia, intensive agriculture poses contamination risks to both surface water and groundwater. Triazine herbicides, extensively used on canola crops and for governmental landscaping and road maintenance, are among the key pollutants (Regional Roads Victoria, 2019). These pesticides directly threaten various aquatic organisms and have significant adverse effects on human health (Schäfer et al., 2011; Cohen, 2007; Sengupta and Banerjee, 2014; Swan, 2006). Atrazine, a commonly used herbicide, has been linked to reduced sperm quality in small mammals and embryonic toxicity (Feyzi Dehkhargani et al., 2011; Bigsby et al., 1999). Despite being permitted in Australia and Canada, atrazine and its mixtures are banned in the European Union (European Commission, 2004), highlighting the need to understand pesticide mobility and impacts (Kearney and Helling, 1982).

The Glenelg Hopkins Catchment (GHC), spanning over 26,000 km2, is predominantly used for agriculture, with 80% allocated to agricultural activities (VLUIS, 2017). While vital for Australian agriculture (GH CMA, 2018), it hosts ecologically significant wetlands like the Victorian Western Districts Lakes (DNRE, 2002b), serving as habitats for threatened species (CMA, 2014). Some wetlands rely on groundwater, making them susceptible to fluctuations in quality (GH CMA, 2006). Despite their ecological significance, there's a dearth of research on the impact of agricultural practices on groundwater and wetlands within this catchment. Although some studies explored groundwater nutrients' effects on wetlands, inconclusive results were attributed to small sample sizes (Raisin, Bartley, and Croome, 1999). Notably, the Victorian Strategic Direction Statement overlooks agricultural pollution in groundwater as a threat to wetlands.

Over the past two decades, triazine-based products' use in Victorian agriculture has surged, particularly with canola production (VLUIS). Multiple herbicide and fungicide applications are made throughout the cropping season, emphasizing reliance on these chemicals for pest management. Herbicides recommended by Regional Roads Victoria for road conservation purposes also pose risks to aquatic ecosystems, jeopardizing wetlands and contributing to algal blooms (Rabalais, 2002). The active chemical ingredients of these herbicides are listed in Table 1.

Table 1

Commercial herbicides with their chemical active ingredients (Conboy, Jhonson, Mclean et al., 2018)
Altiplano	Triflur	Atradex/ Atrazine	Ultra	Avadex	Burst	Butisan
Clomazone, Napropamide	Trifluralin, Liquid hydrocarbon	Atrazine	Potassium salt of glyphosate	Triallate, Liquid Hydrocarbon	Propyzamide	Metazachlor

Despite sporadic efforts, studies investigating pesticide and nutrient pollution in Victoria are scarce. Most pesticide studies in groundwater date back to before 2007, necessitating updated assessments given escalating pesticide usage trends. Recent reviews identified atrazine, simazine, chlorpyriphos, and DDT as commonly detected pesticides in Victoria, reflecting international trends like New Zealand's national pesticide survey. However, nutrient data gaps exacerbate pesticide contamination assessment challenges. Financial and logistical constraints, coupled with the absence of specific guidelines for groundwater pesticide surveys, hinder robust assessments. Despite acknowledgments of the need for hydrogeological risk assessments, the lack of comprehensive guidelines for estimating aquifer vulnerability underscores the need for standardized methodologies.

This study aims to assess agriculture's impact on groundwater quality in shallow aquifers and wetlands within the study area. Water samples from high, medium, and low-risk zones were analyzed for triazine herbicides, nitrogen, phosphorus, pH, temperature, and electrical conductivity.

2.1. Sample size

We identified a total of 47 monitoring bores and 10 wetlands for our study. However, out of the 47 selected monitoring bores, 24 were found to be inaccessible due to various reasons, such as being situated on private land, having an internal diameter less than 60mm, or being physically inaccessible. Therefore, only 23 bores were accessible for testing. The findings from the field survey are summarized in Table 2.

Table 2

Sample size, the GH CMA
Sample size and total monitoring bores
47 Total sites visited
24 Bores were inaccessible or with no water
17 Bores visited in the first field survey
6 Bores were sampled in the second field survey
10 Wetlands

Areas with the lowest vulnerability values were observed in the Grampians National Park and the eastern region of the study area, encompassing areas between Casterton, Coleraine, and Merino. Conversely, the most vulnerable regions were situated along the ocean side and in the area between the Grampians, Dunkeld, Ararat, and Skipton. It is noteworthy that this latter region also serves as the primary agricultural production hub within the catchment.

2.2. Groundwater monitoring bores and wetlands selection

After filtering the water from the SOBN monitoring bores, we identified 351 active monitoring bores suitable for testing. Overlaying the land use map with the SOBN map aided in identifying areas and monitoring bores susceptible to agricultural pollution, as illustrated in Fig. 3. Wetlands were selected based on the land use map, which delineated areas designated for canola cropping. Consequently, a total of 23 bores and 10 wetlands were selected across the GHC.

2.3. Groundwater nutrient results

Groundwater samples underwent analysis to determine the concentrations of NOx and DRP, serving as pollution indicators. The findings revealed elevated pollution levels at several bore locations. NOx concentrations ranged from 0.04 mg/L to 51.6 mg/L, with bore 112233 exhibiting the highest concentration, surpassing the Australian threshold value for nitrogen as NOx in freshwater (0.04 mg/L). Similarly, DRP concentrations varied from 0.015 mg/L to 0.30 mg/L, with bore 112233 also recording the highest concentration, exceeding the Australian trigger value of 0.015 mg/L specified for slightly disturbed ecosystems in lowland river ecosystems, as outlined in Table 3 of the ANZECC/ARMCANZ (2000) guidelines. These outcomes indicate a considerable proportion of bores exhibiting NOx and DRP pollution concentrations above threshold values, signifying a potential risk of groundwater contamination. Bore 98253, situated outside the study area in a confined aquifer, was excluded from linear correlation analysis.

Table 3

Results for NOx and DRP in GW bores
N	Bore ID	NOx	DRP	N	Bore ID	NOx	DRP
1	11170	6.54	0.02	12	111528	< 0.01	0.08
2	45807	0.52	0.04	13	111530	0.08	0.06
3	82181	< 0.01	< 0.01	14	111690	0.02	0.01
4	83447	0.12	< 0.01	15	111696	0.03	0.09
5	87757	0.03	< 0.01	16	112232	2.17	0.11
6	98253	0.25	0.01	17	112233A	51.6	0.30
7	102412	< 0.01	< 0.01	18	112237	0.06	0.03
8	102621	1.16	< 0.01	19	141235	0.01	< 0.01
9	103343	4.20	< 0.01	20	141307	4.37	0.07
10	110108	2.49	0.08	21	146024	< 0.01	< 0.01
11	111527	1.00	< 0.01	22	146025	< 0.01	< 0.01
				23	112233B	2.53	< 0.01

2.4. Groundwater triazines results

Table 4 presents the outcomes of herbicide analysis conducted on groundwater samples. Among the 23 monitoring bores examined, only bore 112233 exhibited traces of pesticides. Subsequently, a follow-up field survey was undertaken for this bore, treating the second sampling as an independent sample. Notably, no pesticides were detected during the second sampling of bore 112233. The reporting limit for triazines was approximately 0.1 µg/L, and the total concentration observed in this bore was 19.52 µg/L in August 2017. However, upon revisiting the location in April 2018, no traces of triazines were detected, as depicted in the table. Further laboratory analyses unveiled an excessive presence of coal attributed to the burning of agricultural paddocks situated approximately 800m away from the groundwater monitoring bore. Agricultural land burning is a common practice employed to clear remnants of previous crop plants. The resulting coal acts as active carbon, effectively adsorbing pollutants, including nutrients and herbicides.

Table 4

Groundwater triazine concentrations [µg/L]
N	Bore ID	Atrazine	Hexazinone	Metribuzin	Prometryn	Simazine	Desisopropyl-atrazine	Desethyl-atrazine
17	112233A	0.017	< 0.01	6.3	< 0.01	0.12	13	< 0.1
23	112233B	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1

2.5. Wetlands nutrients results

Table 5 illustrates the outcomes of nutrient analysis conducted in wetlands. The majority of nutrient concentrations were observed to fall below the threshold values delineated in the ANZECC/ARMCANZ (2000) wetlands water quality guidelines. For instance, Victorian guidelines specify threshold values of 0.04 mg/L for NOx and 0.015 mg/L for DRP in inland lakes (EPA, 2010). Apart from a few exceptions (Bull Rush, Lake Bookar, and Linlithgow), where DRP values slightly exceeded 0.015 mg/L, the phosphorus concentrations remained within acceptable limits. It is crucial to recognize that the limit of detection for nutrients was approximately 0.01 mg/L, and the results represent a single sampling point within the littoral zone. Given these constraints, caution is warranted when interpreting the nutrient concentration findings in wetlands.

Table 5

Wetlands nutrients results [mg/L]
Wetland	NOx (mg/L)	DRP (mg/L)
Bull rush	< 0.01	0.16
Buninjon Lake	< 0.01	0.02
Cobden Terang Volcanic	< 0.01	< 0.01
Dergholm Park	< 0.01	< 0.01
Lake Bookar	0.04	0.47
Lake Kennedy	< 0.01	0.09
Linlithgow	< 0.01	0.22
Maroona Wetland	0.05	< 0.01
Rookies Hill	0.05	0.02
Yatmarone Wetland	0.02	< 0.01

Traces of the herbicides atrazine and simazine were identified in five wetlands. Atrazine was detected in Bull Rush, Lake Kennedy, and Dergholm Park, with concentrations of 0.049 µg/L, 0.064 µg/L, and 0.036 µg/L, respectively. Simazine, on the other hand, was found in Bull Rush, Lake Kennedy, Buninjon Lake, and Lake Bookar, with concentrations approximately at 0.16 µg/L, 1.2 µg/L, 0.064 µg/L, and 0.097 µg/L, respectively. A summary of atrazine and simazine presence in selected wetlands within the GH CMA is provided in Table 6, with Lake Kennedy exhibiting the highest concentrations for both atrazine (0.064 µg/L) and simazine (1.2 µg/L).

The AANZECC/ARMCANZ (2000) guidelines establish freshwater ecosystem thresholds of 13.0 µg/L for atrazine and 3.2 µg/L for simazine. All detected concentrations fell below these thresholds. However, it is important to exercise caution as the measurements were derived from single-point samples within the littoral zone. Among the wetlands surveyed, atrazine contamination was evident in 30%, while simazine was present in 40% of the wetlands.

Table 6

Triazine detection in wetlands at the GH CMA, Victoria, Aus. (µg/L)
Wetland	Atrazine	Hexazinone	Metribuzin	Prometryn	Simazine	Desisopropyl-atrazine	Desethyl-atrazine
Bull Rush	0.049	< 0.01	< 0.01	< 0.01	0.16	< 0.1	< 0.1
Lake Kennedy	0.064	< 0.01	< 0.01	< 0.01	1.2	< 0.1	< 0.1
Buninjon Lake	< 0.01	< 0.01	< 0.01	< 0.01	0.064	< 0.1	< 0.1
Cobden Terang	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.1	< 0.1
Dergholm Park	0.036	< 0.01	< 0.01	< 0.01	< 0.01	< 0.1	< 0.1
Lake Bookar	< 0.01	< 0.01	< 0.01	< 0.01	0.097	< 0.1	< 0.1
Linlithgow	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.1	< 0.1
Yatmarone	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.1	< 0.1
Rookie Hills	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1
Maroona	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1	< 0.1

This study reveals the impact of agricultural activities on groundwater within the GHC region. Among the 23 sampled bores, 65% (15 out of 23) exhibited NOx concentrations surpassing Australian guideline thresholds, while 43.47% (10 out of 23) exceeded the threshold values for DRP. Notably, Bore 112233 displayed notably high concentrations of total triazine herbicides, including atrazine, metribuzin, simazine, and desethyl-atrazine. Despite representing the 4.3 percentile of the sample size, its elevated triazine levels underscore its significance in assessing groundwater pollution dimensions.

In terms of wetland ecosystems, nutrient levels were generally within acceptable limits, aligning with Victorian Lakes trigger values for nitrogen as NOx and phosphorus as DRP. However, herbicide contamination was observed, with atrazine detected in 30% (3 out of 10) of the wetlands and simazine in 40% (4 out of 10). It is worth noting that the wetland sampling methodology may not fully capture ecosystem-wide pesticide exposure, warranting further investigation into pesticide sources.

The identification of nutrient and pesticide contamination in a single bore suggests the potential risk of aquifer pollution from agrochemicals. The fluctuating occurrence of pesticides in bore 112233 highlights the complexity of groundwater pollution dynamics, reflecting land management practices by farmers. Thus, further research is imperative to deepen our understanding of groundwater pollution trends in agricultural settings.

Future investigations should focus on elucidating pesticide pathways to groundwater and wetlands at both regional and state levels, employing more comprehensive sampling and monitoring strategies. Addressing the aforementioned limitations underscores the necessity for improved groundwater risk assessment tools.

4.1. Study Area

The Glenelg Hopkins Catchment Management Authority (GH CMA) is situated in the southwestern region of the Victorian State (Fig. 1), bordered by the Wimmera CMA to the north, the Corangamite CMA to the east, South Australia to the west, and the Tasman Sea to the south (CMA, 2013). For a comprehensive understanding of the study area and aquifer's hydrogeological configuration, please consult Cervantes-Servin et al. Groundwater depth in GH Victoria, Australia, varies seasonally, with the water table closer to the surface during winter and deeper in summer, typically ranging from 0.0m to 6.0m below the surface on average. The landscape across the 26,000 square kilometres of land is diverse, featuring prominent features like the Grampians National Park, the Flat Volcanic Plains, Central Highlands, and Dundas Tablelands (CMA, 2013; GH CMA, 2018). This area encompasses various land uses, including agriculture, water reservoirs, nature conservation areas, lakes, wetlands, energy production sites, and urban areas. Dominant crops in agriculture include canola, wheat, barley, oats, and winter pastures (Conboy et al., 2018). The GHC ranks among the most productive agricultural regions in Australia, being the fourth CMA nationwide and the top in Victoria for agricultural productivity. In the fiscal year 2017–2018, agricultural production revenue totalled approximately AU$2,184 million (GH CMA, 2018).

4.2. Groundwater monitoring bores

We visited 33 sites, being most of them groundwater bores as seen in Fig. 2. The GHC has more than 351 active groundwater monitoring bores according to the Groundwater Monitoring System of the State Observation Bore Network (SOBN) (http://data.water.vic.gov.au/). In Fig. 2 we can see the location across the study site, to do this we covered the entire Grampians region across the 220 Kilometers length of the region. The State Monitoring Wells were overlaid onto the region map and clipped using ArcMap10.4.

4.3. Wetlands and groundwater sample collection

Water samples were manually collected from wetlands during the period of 2017–2018. Sampling took place at the shoreline of each wetland and within the first 4.0 meters from the waterline. To obtain the samples, a sealed 500ml dark glass bottle was submerged into the water at a depth of 0.5 meters, and the lid was opened to allow water to fill the bottle without oxygen. The specific sampling locations for each wetland are detailed in Table 2. The sampling objective was to gather water samples using simple equipment while still providing strong data of water quality. Samples were handled according to the protocols outlined in "A guide to the sampling and analysis of waters, wastewaters, soils and wastes" (EPA, 2000) and "Sampling and analysis of waters, wastewaters, soils and wastes" (EPA, 2009).

4.4. Groundwater Quality Sampling

Groundwater quality samples were collected and preserved in 500ml dark glass bottles. For each bore, three 500ml bottles were filled with water and kept cool with ice during transportation. Upon arrival, the samples were stored at 4°C in a dark room until laboratory analysis.

The methodology employed for groundwater bore sampling followed the low flow groundwater sampling technique. This method utilized a pneumatic low flow pump (Sample Pro–Micropurge Portable Pump), a water quality multiparameter device (YSI Pro), and a 2.0L probe. The pump was activated using a pneumatic compressor and air controller. Parameters such as pH, temperature, and conductivity were stabilized to ensure accurate groundwater flow. Samples were extracted from the bores in accordance with the Victorian groundwater sampling guidelines (EPA, 2000).

The samples were dispatched to accredited laboratories in Melbourne, Victoria, for analysis. The National Measurement Institute (NMI) conducted the analysis for the initial groundwater sampling campaign, while the Department of Industry, Innovation, and Science at The Australian Government and the Australian Laboratory Services (ALS) conducted the analysis for the subsequent groundwater sampling campaign. The samples underwent testing for nitrogen as NOx (NO²- and NO³-) and phosphorus as dissolved reactive phosphorus (DRP) using the discrete analyser method. Additionally, the samples were examined for the triazine herbicide suite, comprising atrazine, hexazinone, metribuzin, prometrym, simazine, desisopropyl atrazine, and desisopropyl atrazine. Liquid chromatography was employed to detect the presence of triazine herbicides. The reporting limit for NOx and DRP was 0.01 mg/L, while the reporting limit for the triazine suite was 0.01 µg/L.

Acknowledgments

This research was supported by Melbourne Water, Melbourne School of Engineering at The University of Melbourne, RMIT School of Science at The Royal Melbourne Institute of Technology, and the "Consejo Nacional de Ciencia y Tecnología CONACYT-Mexico" under the International Postgraduate Scholarship Program. We also acknowledge the farmers support and aid at the GH region during this investigation.

Author contributions

A. I. C-S.: Conceptualization; data analysis; funding acquisition; investigation; methodology; resources; writing original draft; review and editing; M. A.: Conceptualization; data analysis; funding acquisition; methodology; resources; supervision; review and editing; J. M.: Data analysis, methodology; V. P.: Conceptualization; data analysis; funding acquisition; methodology; resources; fieldwork supervision, laboratory work supervision; review and editing. By this means, we the authors give legal consent for the publication of this research.

Funding

This research was sponsored by Melbourne Water, Melbourne School of Engineering at The University of Melbourne, The RMIT School of Science at The Royal Melbourne Institute of Technology and The Mexican Council of Science and Technology “Consejo Nacional de Ciencia y Tecnologia (CONACYT)” under the international postgraduate scholarship program.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Additional information

Correspondence and requests for materials should be addressed to A. I. C-S.

Competing interests: The authors declare no competing interests.

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No competing interests reported.

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Groundwater and wetlands contamination with pesticides and nutrients from farms in Victoria, Australia

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Abstract

Figures

1. Introduction

2. Results

2.1. Sample size

2.2. Groundwater monitoring bores and wetlands selection

2.3. Groundwater nutrient results

2.4. Groundwater triazines results

2.5. Wetlands nutrients results

3. Discussion

4. Materials and Methods

4.1. Study Area

4.2. Groundwater monitoring bores

4.3. Wetlands and groundwater sample collection

4.4. Groundwater Quality Sampling

Declarations

References

Additional Declarations

Status:

Version 1